Functional coated product and process for producing the same and the use thereof

ABSTRACT

The present invention provides a functional coated product having excellent adhesion properties of a coating to a substrate, hardly causing the deterioration of the substrate and the coating due to a photocatalyst, hardly having dirt because the smoothness of the surface coating is high, and having high photocatalytic action; a method for producing the same and the use thereof. 
     The coated product of the present invention has the first coating layer comprising a cured coating made of an acryl-modified silicone resin coating material, which is formed on the surface of the substrate, and the second coating layer comprising a cured coating made of a functional coating material containing the photocatalyst, which is formed con the surface of the first coating layer. When producing such a coated product, the acryl-modified silicone resin coating material is applied to the surface of the substrate as the first coating layer and it is semi-cured. After that, a photocatalyst-containing functional coating material is applied to the surface of this first coating layer in a semi-cured condition and then both of the coating layers are cured. Thereby, a coated product having a higher effect can be obtained.

This application is the national phase under 35 U.S.C. §371 of prior PCTInternational Application No. PCT/JP97/04559 which has an Internationalfiling date of Dec. 11, 1997 which designated the United States ofAmerica, the entire contents of which are hereby incorporated byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a functional coated product havingphotocatalytic activity and a process for producing the same and the usethereof.

2. Description of the Prior Art

When a photocatalyst is added to a coating material, the resultingcoating is irradiated by ultraviolet light to exhibits a decomposingeffect of organic substances, deodorizing effect, antifungal effect,etc.

As a coating material having such photocatalytic function, for example,a photocatalytic organic paint in which photocatalytic particles aredispersed in organic resin is known. However, the photocatalyticorganicpaint has a drawback that the coating is deteriorated due toultraviolet rays and photocatalytic function.

An inorganic paint, in which photocatalytic particles are dispersed inan inorganic composition such as a silicate, a phosphate or a zirconate,is known as a coating material having photocatalytic function. Theseinorganic paints have much better durability than that of photocatalyticorganic paints, however, it is necessary to conduct baking at a hightemperature of 200° C. or more. Therefore, the range of usage islimited, and it was not suitable for applying them directly to aconstruction material or plastic which has inferior heat resistance.Further, the silicate inorganic paint has also a drawback that an alkaliwas eluted to cause a whitening phenomenon easily.

In Japanese Patent Publication Laid-Open No. 57470/1987, an inorganicpaint in which a metal alkoxide is contained is disclosed. Thisinorganic paint is cured at a temperature of not more than 200° C.,however, the coating does not have flexibility and there was a problemthat crack easily occurred.

Recently, with a necessity to apply a paint to various materials, alow-temperature curing paint keeping its photocatalytic performance evenif it is used for a long time, having durability in the coating itselfhas been desired.

In Japanese Patent Publication Laid-Open No. 67835/1996, an antifungalinorganic paint containing a photocatalyst, which is a component havinga photocatalytic function as an anti-fungus agent, is proposed. However,when a photocatalyst was supported on a substrate, there was a problemconcerning the limitation of the substrate or adhesion properties.Further, there was a tendency that the photocatalyst was precipitated inthe paint, and the performance of the photocatalyst was not easilyexhibited.

Therefore, in Japanese Patent Publication Laid Open No. 141503/1996, theimprovement in a method for forming an inorganic coating havingphotocatalyst on the surface thereof and high photocatalytic performanceis suggested. This coating has high adhesion to an inorganic substrate,however, it has poor adhesion to the surface of plastic or a materialcoated with an organic substance. Further, a coating of theabove-mentioned inorganic coating lacks in smoothness on the surface,therefore there was a drawback that dirt is easily adhered.

Further, when a paint containing a photocatalyst is directly applied tothe surface of an organic substrate or a substrate coated with anorganic substance, there was a problem that said substrate was easilydeteriorated due to the action of the photocatalyst.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a functional coatedproduct which has excellent adhesion properties to various substrates,hardly causes the deterioration of the substrate and a coating due tothe action of a photocatalyst and also has high photocatalytic function,and a process for producing the same and the use thereof.

The functional coated product of the present invention has the firstcoating layer comprising a cured coating made of an acryl-modifiedsilicone resin coating material, and the second coating layer comprisinga cured coating made of a functional coating material (1) or (2) below.The present invention also provides a production method of thefunctional coated product and use thereof.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The functional coated product of the present invention has a firstcoating layer comprising a cured coating made of an acryl-modifiedsilicone resin coating material, and a second coating layer comprising acured coating made of a functional coating material (1) or (2).

A process for producing a functional coated product of the presentinvention which comprises the following steps:

-   -   forming a first coating layer by applying an acryl-modified        silicone resin coating material to surface of a substrate,    -   forming a semi-cured layer by semi-curing the first coating        layer,    -   forming a second coating layer by applying a functional coating        material (1) or (2) to the semi-cured first coating layer, and    -   curing said semi-cured layer and said second coating layer.

The acryl-modified silicone resin coating material contains thefollowing components (A), (B), (C) and (D).

The functional coating material (1) contains the following components(E) and (F).

The functional coating material (2) contains the following components(A), (B), (C), and (F).

Component (A):

-   a silica-dispersed organosilane oligomer solution obtained by    partially hydrolyzing a hydrolytic organosilane represented by the    general formula    R¹ _(m)SiX_(4-m)  (I)    (wherein R¹ indicates a substituted or non-substituted monovalent    hydrocarbon group having 1 to 8 carbon atoms, which may be the same    or different, m indicates an integer of 0 to 3, and X indicates a    hydrolytic group)    in an organic solvent, water or colloidal silica dispersend in a    mixed solvent thereof, under the condition that 0.001 to 0.5 mol of    water is used based on 1 mol equivalent of the above-mentioned    hydrolytic group (X);    Component (B):-   a polyorganosiloxane represented by the average compositional    formula:    R² _(a)Si(OH)_(b)O_((4-a-b)/2)  (II)    (wherein R² indicates a substituted or non-substituted monovalent    hydrocarbon group having 1 to 8 carbon atoms, which may be the same    or different, a and b separately satisfy the following condition:    0.2≦a≦2, 0.0001≦b≦3, a+b<4),    which contains a silanol group in its molecule;    Component (C):-   a curing catalyst;    Component (D):-   an acrylic copolymer resin of three (meth)acrylate components    represented by the general formula (III):    CH₂═CR³(COOR⁴)  (III)    (wherein R³ is a hydrogen atom and/or a methyl group), comprising    the first (meth)acrylate component in which R⁴ is a substituted or    non-substituted hydrocarbon group having 1 to 9 carbon atoms, the    second methacrylate in which R⁴ is at least one group selected from    the group consisting of an epoxy group, a glycidyl group and a    hydrocarbon group containing at least either of those groups, and    the third methacrylate in which R⁴ is a hydrocarbon group containing    an alkoxy silyl group and/or a halogenated silyl group); and said    acrylic copolymer resin has an average molecular weight of 1,000 to    50,000 (in terms of polystyrene).

In the present specification, (meth)acrylate indicates either acrylateor methacrylate or both of them.

Component (E):

-   an organosiloxane comprising a hydrolytic polycondensate comprising    a mixture of    -   (E1) 5 to 30,000 parts by weight of a silica compound        represented by the general formula:        Si(OR⁵)₄        and/or colloidal silica,    -   (E2) 100 parts by weight of a silica compound represented by the        general formula:        R⁶Si(OR⁵)₃    -   (E3) 0 to 60 parts by weight of a silica compound represented by        the general formula:        R⁶ ₂Si(OR⁵)₂        (wherein R⁵ and R⁶ indicate a monovalent hydrocarbon group) and        said weight-average molecular weight being adjusted to 800 or        more in terms of polystyrene; and        Component (F):-   a photocatalyst.

In the above-mentioned acryl-modified silicone resin coating material,it is preferred that 1 to 94 parts by weight of Component (B) and 5 to35 parts by weight of Component (D) are formulated in 1 to 94 parts byweight of Component (A), based on the solid content of the wholecondensate (provided that the total amount of Components (A), (B) and(D) comes to 100 parts by weight).

The above-mentioned acryl-modified silicone resin coating material maycontain a pigment.

It is preferred that the above-mentioned substrate is selected from thegroup consisting of a metallic substrate, an organic substrate and asubstrate coated with an organic substance in which either one of theabove substrates has a coating formed from an organic substance on thesurface thereof.

The coated product of the present invention can be used for, forexample, a member related to building construction, particularly, anoutdoor member related to building construction, a gate for a building,and a member to be used for that purpose (e.g., a gate pier, etc.), awall for a building and a member to be used for that purpose, a window(e.g., a lighting window, etc.), and a member to be used for thatpurpose (e.g., a window frame, etc.), an automobile, mechanicalequipment, particularly, outdoor mechanical equipment, a member forhighway-related construction, (particularly, a traffic-control sign), apost for public notice, particularly, an outdoor post for public notice,an indoor or outdoor lighting fixture and a member to be used for thatpurpose (e.g., a resin material, a metal material, etc.), by equippingit with at least a part of the above-mentioned materials.

Silica compounds (E1) to (E3), which are used as a raw material ofComponent (E) of the functional coating material (1), can be representedby the general formulaR⁶nSi(OR⁵)_(4-n)  (IV)

Herein R⁵ and R⁶ indicate a monovalent hydrocarbon group, and nindicates an integer of 0 to 2.

R⁶ is not specifically limited, but may be, for example, a substitutedor nonsubstituted monovalent hydrocarbon group having 1 to 8 carbonatoms. Examples thereof include alkyl groups such as methyl groups,ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups,heptyl groups or octyl groups; cycloalkyl groups such as cyclopentylgroups or cyclohexyl groups; aralkyl groups such as 2-phenylethylgroups, 2-phenylpropyl groups, 3-phenylpropyl groups; aryl groups suchas phenyl groups or tolyl groups; alkenyl groups such as vinyl groups orallyl groups; halogen-substituted hydrocarbon groups such aschloromethyl groups or γ-chloropropyl groups or 3,3,3-trifluoropropylgroups; substituted hydrocarbon groups such as γ-methacryloxypropylgroups, γ-glycidyloxypropyl groups, 3,4-epoxycyclohexylethyl groups orγ-mercaptopropyl groups. Among them, alkyl groups and phenyl groupshaving 1 to 4 carbon atoms are preferred because they are easilysynthesized or easily available.

R⁵ is not specifically limited, but alkyl groups having 1 to 4 carbonatoms are used as a main material.

Particularly, examples of the tetraalkoxysilane (in which n=0) includetetramethoxysilane, tetraethoxysilane and the like. Examples of theorganotrialkoxysilane (in which n=1) include methyltrimethoxysilane,methyltriethoxysilane, methyltriisopropoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane,3,3,3-trifluoropropyltrimethoxysilane, etc. Further, examples of thediorganodialkoxysilane (in which n=2) include dimethyldimethoxysilane,dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane,methylphenyldimethoxysilane and the like.

These R⁵ and R⁶ may be the same or different among silica compounds (E1)to (E3).

The above-mentioned organosiloxane (E) can be prepared, for example, bydiluting the raw materials (E1) to (E3) with a suitable solvent, addingthe necessary amount of water and a catalyst as a curing agent thereto,and conducting hydrolysis and polycondensation to prepare a prepolymer.At this occasion, the weight-average molecular weight of the resultingprepolymer is adjusted to 800 or more, preferably 850 or more, morefavorably 900 or more, in terms of polystyrene. At this occasion, it isadjusted so that the upper limit of the molecular weight is not morethan 50,000, preferably 45,000, more favorably 40,000. If thedistribution of molecular weight of the prepolymer (the weight-averagemolecular weight (Mw)) is less than 800, the cure shrinkage at the timeof the polycondensation of the functional coating material is large, andtherefore, crack is liable to occur on the coating after curing.Further, if the molecular weight is more than 50,000, the time for thecuring reaction is required, which may result in an insufficienthardness of the coating.

The amount of raw materials (E1) to (E3) to be used at the time ofpreparing organosiloxane (E) is 5 to 30,000 parts by weight (preferably10 to 25,000 parts by weight, more favorably 20 to 20,000 parts byweight) of (E1), 0 to 60 parts by weight (preferably 0 to 40 parts byweight, more favorably 0 to 30 parts by weight) of (E3), based on 100parts by weight of (E2). If the amount of (E1) used is less than theabove range, there is a problem that the desired hardness of the curedcoating is not obtained (the hardness is lowered). On the other hand, ifit is more than the above range, the crosslinking density of the curedcoating is too high, therefore, there is a problem that crack is liableto occur. Further, if the amount of (E3) used is more than the aboverange, there is a problem that the desired hardness of the cured coatingis not obtained (the hardness is lowered).

Colloidal silica which can be used as a material (E1) is notspecifically limited. For example, water-dispersed or non-aqueousorganic solvent (e.g., alcohol)-dispersed colloidal silica can be used.In general, such colloidal silica contains 20 to 50% by weight of silicaas a solid content. From this value, the amount of silica to beformulated can be determined. Further, when using water-dispersedcolloidal silica, water existing as a component other than the solidcontent can be used as a curing agent as described bellow.Water-dispersed colloidal silica is usually made from water-glass, butit can be easily obtained as a commercially available product.Furthermore, organic solvent-dispersed colloidal silica can be easilyprepared by replacing the water in the above-mentioned water-dispersedcolloidal silica with an organic solvent. Such organic solvent-dispersedcolloidal silica can be easily obtained as a commercially availableproduct. In the organic solvent-dispersed colloidal silica, the kind ofthe organic solvent, in which colloidal silica is dispersed, is notspecifically limited. Examples thereof include lower aliphatic alcoholssuch as methanol, ethanol, isopropanol, n-butanol or isobutanol;ethylene glycol derivatives such as ethylene glycol, ethylene glycolmonobutyl ether or ethylene acetate glycol monoethyl ether; diethyleneglycol derivatives such as diethylene glycol or diethylene glycolmonobutyl ether; and diacetone alcohols, etc. One or two or moresolvents selected from the above groups can be used. Together with thesehydrophilic organic solvents, toluene, xylene, ethyl acetate, butylacetate, methyl ethyl ketone, methyl isobutyl ketone, methyl ethylketoxime and the like can also be used.

Further, water is used as a curing agent at the time of the hydrolyticpolycondensation reaction. The amount of water is preferably 0.01 to 3.0mol, more favorably 0.3 to 1.5 mol, based on 1 mol equivalent of OR⁵groups of silica compounds (E1) to (E3).

A diluting solvent to be used at the time of the hydrolyticpolycondensation reaction of raw materials (E1) to (E3) is notspecifically limited. For example, those which were described as adispersing solvent of colloidal silica can be used.

Further, a pH value of the above-mentioned organosiloxane (E) is notspecifically limited. It is preferred to adjust it in the range between3.8 and 6. If the pH value is within this range, it is possible to useorganosiloxane (E) stably within the above-mentioned molecular weight.When the pH value is out of the above range, the stability oforganosiloxane (E) is deteriorated, therefore, the available term aftera paint is prepared is limited. Herein, a method of adjusting a pH valueis not specifically limited. For example, if the pH value is less than3.8 at the time of mixing raw materials of organosiloxane (E), the pHvalue is adjusted to within the above-mentioned range using a basicreagent such as ammonia. If the pH value exceeds 6, it may be adjustedusing an acidic reagent such as hydrochloric acid. Further, depending onthe pH value, the molecular weight remains small and the reaction doesnot proceed, therefore, it takes a long time to reach theabove-mentioned range of the molecular weight. In that case,organosiloxane (E) may be heated to accelerate the reaction. Further,after making the reaction proceed using an acidic reagent to reduce thepH value, the pH value may be increased to the predetermined value usinga basic reagent.

It is not necessary that a functional coating material (1) contains acuring catalyst when it is cured by heating; however, the functionalcoating material (1) may optionally contain such a catalyst in order toaccelerate the heat-curing of an applied coating or to cure the appliedcoating at a normal temperature by accelerating the polycondensationreaction of organosiloxane (E). The curing catalyst is not specificallylimited. Examples thereof include alkyl titanates; metal salts ofcarboxylic acid such as tin octylate, dibutyltin dilaurate or dioctyltindimaleate; amine salts such as dibutylamine-2-hexoate, dimethylamineacetate or ethanolamine acetate; quaternary ammonium salts of carboxylicacid such as tetramethylammonium acetate; amine salts such astetraethylpentamine; amine-type silane coupling agents such asN-β-aminoethyl-γ-aminopropyltrimethoxysilane orN-β-aminoethyl-γ-aminopropylmethyldimethoxysilane; acids such asp-toluenesulfonic acid, phthalic acid or hydrochloric acid; aluminumcompounds such as aluminum chelate; alkali metal salts such as lithiumacetate, potassium acetate, lithium formate, sodium formate, potassiumphosphate or potassium hydroxide; titanium compounds such astetraisopropyl titanate, tetrabutyl titanate or titanium tetraacetylacetonate; halogenated silanes such as methyl trichlorosilane,dimethyldichlorosilane or trimethylmonochlorosilane. However, inaddition to them, other curing catalysts may be contained as long asthey are useful for the acceleration of the condensation reaction oforganosiloxane (E).

When the functional coating material (1) also contains a curing catalyst(C), it is preferable to use not more than 25% by weight, more favorablynot more than 20% by weight of the curing catalyst, based on the solidcontent of the whole condensate of organosiloxane (E). If it is morethan 45% by weight, storage stability of the coating solution may bedeteriorated.

The photocatalyst to be used as Component (F) for functional coatingmaterials (1) and (2) (a photocatalyst (F)) is not specifically limited.Examples thereof include oxides such as titanium oxide, zinc oxide, tinoxide, zirconium oxide, tungsten oxide, chromium oxide, molybudenumoxide, iron oxide, nickel oxide, ruthenium oxide, cobalt oxide, copperoxide, manganese oxide, germanium oxide, lead oxide, cadmium oxide,vanadium oxide, niobium oxide, tantalum oxide, rhodium oxide or rheniumoxide. Among them, titanium oxide, zinc oxide, tin oxide, zirconiumoxide, tungsten oxide, iron oxide, niobium oxide are preferred becausethey show activity even if the bake-curing is conducted at a lowtemperature of not more than 100° C. The particularly preferred istitanium oxide. If the transparency of the coating is needed, it ispreferred that the average diameter of the primary particle is not morethan 50 μm, more favorably not more than 5 μm, most favorably not morethan 0.5 μm. One photocatalyst may be used for the photocatalyst (F).Also, two or more catalyst may be used in combination thereof.

It is known that a photocatalyst generates active oxygen (photocatalyticproperties) when ultraviolet is irradiated in the atmosphere. The activeoxygen can oxidize and decompose organic substances. Therefore,utilizing the properties of such a catalyst, a self-cleaning effect ofthe decomposition of dirt originating in carbon, which is adhered to acoated product, (e.g., a carbon component contained in the exhaust gasof an automobile, nicotine of tobacco); a deodorizing effect of thedecomposition of a malodorous component represented by an amine compoundand an aldehyde compound; and an antifungal effect of the prevention ofthe generation of bacteria represented by Escherichia coli andStaphylococcus aureus and the like can be obtained. Further, dirt suchas water repellant organic substances adhered to the surface of acoating is decomposed and removed by the photocatalyst (F). Thereby,there is an effect that wettability of the coating to water is improved.This effect is exhibited regardless of the size of the coating thicknessor the amount of the photocatalyst contained therein.

The photocatalyst (F) may be the one in which a metal is incorporated.The metal to be incorporated is not specifically limited. Examplesthereof include gold, silver, copper, iron, zinc, nickel, cobalt,platinum, ruthenium, palladium, rhodium, cadmium and the like. Amongthem, one or two or more can be suitably used. By the incorporation ofthe metal, the charge separation of the photocatalyst (F) isaccelerated. Therefore, the photocatalytic function is exhibited moreeffectively. The photocatalyst (F) in which a metal is incorporated hasan oxidizing ability in the presence of light. By this oxidizingperformance, the deodorizing effector anti-fungal effect is exhibited.Further, a clay crosslinking material in which the photocatalyst (F) isincorporated between layers. By introducing the photocatalyst betweenthe layers, fine particles are incorporated in the photocatalyst (F) toimprove the photocatalytic performance.

The method for dispersing the photocatalyst (F) in the functionalcoating material (1) or (2) is not specifically limited.

A silica-dispersed organosilane oligomer solution (A) to be used asComponent (A) in the acryl-modified silicone resin coating material orthe functional coating material (2) is a main component of a basepolymer having a hydrolytic group (X) as a functional group which isinvolved with the curing reaction at the time of forming a curedcoating. This can be obtained, for example, by adding one or two or morehydrolytic organosilane compounds represented by the general formula (I)to the colloidal silica dispersed in an organic solvent or water (amixture of the organic solvent and water may be included) and partiallyhydrolyzing the hydrolytic organosilane, under the condition that 0.001to 0.5 mol of water (water which may be contained in the colloidalsilica beforehand and/or added separately.) is used based on 1 molequivalent of the above-mentioned hydrolytic group (X).

R¹ represented by the above-mentioned general formula (I) in thehydrolytic organosilane is not specifically limited as long as it issubstituted or nonsubstituted hydrocarbon group having 1 to 8 carbonatoms. R¹ may be the same or different. Examples thereof include alkylgroups such as methyl groups, ethyl groups, propyl groups, butyl groups,pentyl groups, hexyl groups, heptyl groups or octyl groups; cycloalkylgroups such as cyclopentyl groups or cyclohexyl groups; aralkyl groupssuch as 2-phenylethyl groups, 2-phenylpropyl groups, 3-phenylpropylgroups; aryl groups such as phenyl groups or tolyl groups; alkenylgroups such as vinyl groups or allyl groups; halogen-substitutedhydrocarbon groups such as chloromethyl groups or γ-chloropropyl groupsor 3,3,3-trifluoropropyl groups; substituted hydrocarbon groups such asγ-methacryloxypropyl groups, γ-glycidyloxypropyl groups,3,4-epoxycyclohexylethyl groups or γ-mercaptopropyl groups. Among them,alkyl groups having 1 to 4 carbon atoms and phenyl groups are preferredbecause they are easily synthesized or easily available.

In the above-mentioned general formula (I), the hydrolytic group X isnot specifically limited. For example, an alkoxy group, an acetoxygroup, an oxime group, an enoxy group, an amino group, an aminoxy group,an amide group and the like are included. Among them, an alkoxy group ispreferred because it is easily available and a silica-dispersedorganosilane oligomer solution (A) is easily prepared.

Examples of the above-mentioned hydrolytic organosilane include thosewhich are represented by the above general formula (I) wherein m is aninteger of 0 to 3, i.e., such as those having a mono-, di-, tri- ortetra-functionality. Concrete examples thereof include alkoxysilanes,acetoxysilanes, oximesilanes, enoxysilanes, aminosilanes,aminoxysilanes, amidesilanes and the like. Among them, the preferred arealkoxysilanes because they are easily available and a silica-dispersedorganosilane oligomer solution (A) is easily prepared.

Among alkoxysilnes, particularly, examples of tetraalkoxysilanes whereinm=0 include tetramethoxysilane, tetraethoxysilane and the like. Examplesof the organotrialkoxysilane wherein m=1 include methyltrimethoxysilane,methyltriethoxysilane, methyltriisopropoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane,3,3,3-trifluoropropyltrimethoxysilane and the like. Further, examples ofthe diorganodialkoxysilane wherein m=2 include dimethyldimethoxysilane,dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane,methyl phenyl dimethoxysilane and the like. Examples of thetriorganoalkoxysilane wherein m=3 include trimethylmethoxysilane,trimethylethoxysilane, trimethylisopropoxysilane,dimethylisobutylmethoxysilane and the like. Further, those which aregenerally referred to as silane coupling agents are included inalkoxysilanes.

Among these hydrolytic organosilanes represented by the above-mentionedgeneral formula (I), 50 mole % or more, preferably 60 mol % or more,more favorably 70 mol % or more, may be those having a tri-functionalitywherein m=1. If it is less than 50 mol %, the sufficient coatinghardness cannot be obtained, and also, the dry curability tends to beinferior.

Colloidal silica contained in Component (A) has an effect of enhancinghardness of cured coating of the coating material and improvingsmoothness and crack-arresting ability. The colloidal silica is notspecifically limited. For example, those mentioned as a raw material(E1) of organosiloxane (E) can be used. When using water-dispersedcolloidal silica, water, which is present as a component other than thesolid content, can be used for the hydrolysis of the above-mentionedhydrolytic organosilane. Also, it can be used as a curing agent of thecoating material.

In Component (A), colloidal silica is contained, as a silica content,preferably in an amount of 5 to 95% by weight, more favorably 10 to 90%by weight, most favorably 20 to 80% by weight, based on the solidcontent of the whole condensate of organosilane (I). When the content isless than 5% by weight, the desired coating hardness is not likely to beobtained. On the other hand, when it exceeds 95% by weight, uniformdispersion of silica is difficult, which may cause various problems suchas the gelation of Component (A), or the frequent occurrence of crack inthe cured coating because it is too hard.

Further, in the present specification, the formulation ratio ofComponent (A) in the coating material is a value including a dispersionmedium of colloidal silica.

The amount of water to be used at the time of preparing asilica-dispersed organosilane oligomer solution (A) is 0.001 to 0.5 mol,preferably 0.01 to 0.4 mol, based on 1 mol equivalent of the hydrolyticgroup (X) that the above-mentioned hydrolytic organosilane has. If theamount of water to be used is less than 0.001 mol, a sufficientlypartially hydrolyzed compound is not obtained. If it exceeds 0.5 mol,the stability of the partially hydrolyzed compound is deteriorated.Herein, the above-mentioned amount of water used in the partialhydrolytic reaction of the hydrolytic organosilane is the amount ofwater which is separately added when using the colloidal silicacontaining no water (e.g., the colloidal silica in which an organicsolvent alone is used as a dispersion medium). When using colloidalsilica containing water (e.g., the colloidal silica in which water aloneor a mixture of water and an organic solvent is used as a dispersionmedium), the above-mentioned amount of water is the amount of waterwhich is contained in the colloidal silica beforehand plus at least theamount of water which is contained in the colloidal silica along withthe separately added water. If the amount of water contained in thecolloidal silica beforehand alone satisfies the above-mentioned amountto be used, it is not necessary to add water separately. However, if theamount of water contained in the colloidal silica beforehand alone doesnot satisfy the above-mentioned amount to be used, it is necessary toadd water separately until the amount of water satisfies theabove-mentioned amount to be used. In that case, the amount of theabove-mentioned water to be used is the total amount of the watercontained in the colloidal silica beforehand and the water which isadded separately. Further, even if the water contained in the colloidalsilica alone satisfies the above-mentioned amount to be used, water maybe added separately. In that case, the amount of the above-mentionedwater to be used is also the total amount of the water contained in thecolloidal silica beforehand and the water which is added separately.However, water is added separately so that the total amount does notexceed the above-mentioned upper limit (0.5 mol based on 1 molequivalent of the hydrolytic group (X)).

The method for conducting partial hydrolysis of hydrolytic organosilaneis not specifically limited. For example, hydrolytic organosilane andcolloidal silica may be mixed (when no water is contained or thenecessary amount of water is not contained in the colloidal silica,water is added to that). In that case, partial hydrolytic reactionproceeds at room temperature. In order to accelerate the partialhydrolytic reaction, the mixture may be optionally heated (e.g., at 60to 100° C.) or a catalyst may be used. This catalyst is not specificallylimited. One or two or more organic acids and inorganic acids, such ashydrochloric acid, acetic acid, halogenated silane, chloroacetic acid,citric acid, benzoic acid, dimethylmalonic acid, formic acid, propionicacid, glutaric acid, glycolic acid, maleic acid, malonic acid,toluenesulfonic acid or oxalic acid, can be used.

It is preferred that a pH value of Component (A) is from 2.0 to 7.0,more favorably 2.5 to 6.5, most favorably 3.0 to 6.0, in order to obtainits performance stably for a long period of time. If the pH value is outof this range, particularly, when the amount of water to be used is 0.3mol or more, based on 1 mol equivalent of the hydrolytic group (X), theperformance of Component (A) is not maintained and it is remarkablydeteriorated. If the pH value of Component (A) is out of theabove-mentioned range, e.g., if it is in the acidic side from this;range, a basic reagent such as ammonia or ethylenediamine may be addedto adjust the pH value. If it is in the basic side from this range, anacidic reagent such as hydrochloric acid, nitric acid or acetic acid maybe added to adjust the pH value. However, the adjusting method is notspecifically limited.

A silanol group-containing polyorganosiloxane (B) to be used as theComponent (B) in an acryl-modified silicone resin coating material and afunctional coating material (2) is a crosslinking agent for forming athree-dimensional crosslinking structure in a cured coating by thecondensation reaction with Component (A), which is a base polymer havinga hydrolytic group serving as a functional group in the curing reaction.Component (B) has an effect of absorbing the distortion due to the cureshrinkage of Component (A) and preventing the occurrence of crack.

R² in the above-mentioned average compositional formula (II)representing (B) is not specifically limited, and the same groups as R¹in the above-mentioned formula (I) are exemplified. Preferred examplesthereof include substituted hydrocarbon groups such as alkyl groupshaving 1 to 4 carbon atoms, phenyl groups, vinyl groups,γ-glycidyloxypropyl groups, γ-methacryloxypropyl groups, γ-aminopropylgroups or 3,3,3-trifluoropropyl groups. More favorably, methyl groupsand phenyl groups are included. Further, in the above-mentioned formula(II), a and b are numbers which separately satisfy the above-mentionedcondition. If a is less than 0.2 or b is more than 3, there is troublesuch as the occurrence of crack in the cured coating. Further, if a ismore than 2 and less than 4, or b is less than 0.0001, the curing doesnot proceed favorably.

The silanol group-containing polyorganosiloxane (B) is not specificallylimited. For example, it can be obtained by hydrolyzing, for example,methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane,diphenyldichlorosilane, or a mixture of one or 2 or more alkoxysilanescorresponding to the above-mentioned compounds, using a large amount ofwater according to a known method. The polyorganosiloxane thus obtainedis adjusted so that it has an average-molecular weight (Mw) in terms ofpolystyrene of 700 to 20,000, preferably 750 to 18,000, more favorably800 to 16,000.

In order to obtain the silanol group-containing polyorganosiloxane (B),when an alkoxysilane is hydrolyzed according to a known method, thesmall amount of alkoxy groups which are not hydrolyzed may remain.Namely, polyorganosiloxane containing both silanol groups and the verysmall amount of alkoxy groups is sometimes obtained. In the presentinvention, such polyorganosiloxane may be used.

A curing agent (C) to be used as Component (C) in an acryl-modifiedsilicone resin coating material and a functional coating material (2)accelerates the condensation reaction of Component (A) with Component(B) to cure the coating. Examples of the curing catalyst (C) include allof those which may be optionally contained in the functional coatingmaterial (1) mentioned above. However, the curing catalyst (C) is notspecifically limited as long as it is useful for the acceleration of thecondensation reaction of Component (A) with Component (B), in additionto the above-mentioned catalysts.

Acrylic resin (D) contained in the acryl-modified silicone resin coatingmaterial, which is to be used as Component (D), has an effect ofimproving the toughness of the cured coating made of the acryl-modifiedsilicone resin coating material. Thereby, the occurrence of crack isprevented and it makes it possible to thicken the coating. Further, theacrylic resin (D) is incorporated into a crosslinking condensate ofComponent (A) and Component (B), which is to be a three-dimensional bonestructure of the cured coating made of the acryl-modified silicone resincoating material, to make the crosslinking condensate acryl-modified.When the above-mentioned crosslinking condensate is acryl-modified, theadhesion properties between the cured coating made of the acryl-modifiedsilicone resin coating material and the substrate are improved. Both thecured coating made of the acryl-modified silicone resin coating materialand that made of the functional coating material (1) or 2) are siliconeresin cured products having a polysiloxane structure, therefore, theadhesion properties between both of the coatings are high. For thatreason, between the cured coating of the functional coating material (1)or (2) and the substrate, a cured coating made of the acryl-modifiedsilicone resin coating material having high adhesion properties to themis to be interposed, which eventually improves the adhesion propertiesbetween the cured coating of the functional coating material (1) cr (2)and the substrate. Further, the acryl-modified silicone resin shows highweathering resistance and durability, therefore, it is not influenced bya photocatalyst contained in the functional coating materials (1) and(2), which are on the upper layer.

Examples of the first (meth)acrylate in the above-mentioned formula(III), which is one of the compositional monomers of the acrylic resin(D), include the ones in which R⁴ is represented by at least onesubstituted or nonsubstituted monovalent hydrocarbon group having 1 to 9carbon atoms, for example, alkyl groups such as methyl group, ethylgroup, n-propyl group, i-propyl group, n-butyl group, i-butyl group,sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptylgroup or octyl group; cycloalkyl groups such as cyclopentyl group orcyclohexyl group; aralkyl groups such as 2-phenylethyl group,2-phenylpropyl group or 3-phenylpropyl group; aryl groups such as phenylgroup or tolyl group; halogenated hydrocarbon groups such aschloromethyl group, γ-chloropropyl group or 3,3,3-trifluoropropyl group;hydroxy hydrocarbon groups such as 2-hydroxyethyl group. The preferredare ethyl group, propyl group and butyl group. The first (meth)acrylatein the above-mentioned formula (III) may be a mixture thereof.

Examples of the second (meth)acrylate in the above-mentioned generalformula (III), which is another compositional monomers of the acrylicresin (D), include the ones in which R⁴ is represented by a groupselected from the group consisting of epoxy groups, glycidyl groups andhydrocarbon groups (e.g., γ-glycidyloxypropyl groups, etc.) containingat least either of the above. The preferred are epoxy groups andglycidyl groups. The second (meth) acrylate in the above-mentionedformula (III) may be a mixture thereof.

Examples of the third (meth)acrylate in the above-mentioned generalformula (III), which is one more another compositional monomers of theacrylic resin (D), include the ones in which R⁴ is represented by ahydrocarbon group containing an alkoxysilyl group and/or a halogenatedsilyl group, the hydrocarbon group being exemplified bytrimethoxysilylpropyl group, dimethoxymethylsilylpropyl group,monomethoxydimethylsilylpropyl group, triethoxysilylpropyl group,diethoxymethylsilylpropyl group, ethoxydimethylsilylpropyl group,trichlorosilylpropyl group, dichloromethylsilylpropyl group,chlorodimethylsilylpropyl group, chlorodimethoxysilylpropyl groupsb anddichloromethoxysilylpropyl groups. The preferred aretrimethoxysilylpropyl groups, dimethoxysilylpropyl group andtriethoxysilylpropyl group. The third (meth)acrylate in theabove-mentioned formula (III) may be a mixture thereof.

The acrylic resin (D) is a (meth)acrylate copolymer of at least threekinds of monomers comprising at least one of the first (meth)acrylates,at least one of the second (meth) acrylates and the at leastr one ofthird (meth)acrylates. The acrylic resin (D) may be a copolymer furthercontaining one or two or more methacrylates selected from theabove-mentioned first, second and third methacrylates, or it may also bea copolymer further containing one or two or more methacrylates selectedfrom those other than the above-mentioned methacrylates.

The above-mentioned first (meth)acrylate is an essential component forimproving the toughness of the cured coating of the acryl-modifiedsilicone resin coating material. Further, it also has an effect ofimproving the compatibility between Component (A) and Component (B). Inorder to obtain a greater effect of them, it is preferred that thesubstituted or nonsubstituted hydrocarbon group of R⁴ has a volume atleast to some degree. Therefore, the number of carbon atoms ispreferably 2 or more.

The second (meth)acrylate is an essential component for improving theadhesion properties between the cured coating made of the acryl-modifiedsilicone resin coating material and the substrate.

The third (meth)acrylate forms a chemical bond between the acrylic resin(D) and Components (A) and (B) at the time of curing the coating made ofthe acryl-modified silicone resin coating material. Thereby, the acrylicresin (D) is set in the cured coating. Further, the third (meth)acrylatealso has an effect of improving the compatibility between the acrylicresin (D) and Components (A) and (B).

The molecular weight of the acrylic resin (D) greatly relies on thecompatibility between the acrylic resin (D) and Components (A) and (B).When the weight-average molecular weight of the acrylic resin (D)exceeds 50,000 in terms of polystyrene, phase separation occurs, and thewhitening of the coating may occur. Accordingly, it is preferred thatthe weight-average molecular weight of the acrylic resin (D) is not morethan 50,000 in terms of polystyrene. Further, it is preferred that thelower limit of the weight-average molecular weight of the acrylic resin(D) is 1,000 in terms of polystyrene. If the molecular weight is lessthan 1,000, the toughness of the coating is deteriorated, and crack isliable to occur, which is not preferred.

It is preferred that the second (meth)acrylate is contained in thecopolymer of the acrylic resin (D) in a monomer molar ratio of 2% ormore. If it is less than 2%, the adhesion properties of the coatingtends to be insufficient.

It is preferred that the third (meth)acrylate is contained in thecopolymer in a monomer molar ratio of 2 to 50%. If it is less than 2%,the compatibility between the acrylic resin (D) and Components (A) and(B) is poor and the whitening of the coating may occur. On the otherhand, if it is more than 50%, the bonding density is too high, andtherefore there tends to be no apparent improvement in the toughness, animprovement of which is an original object of the acrylic resin.

The synthesis of the acrylic resin (D) can be conducted, for example, bya solution polymerization method in an organic solvent, an emulsionpolymerization method, a radical polymerization method, a suspensionpolymerization method, an anion polymerization method, a cationpolymerization method or the like. However it is not limited to theabove.

In the radical polymerization method using solution polymerization, itis conducted according to a known method. For example, theabove-mentioned first, second third (meth)acrylate monomers aredissolved in an organic solvent in a reaction container. Further, aradical polymerizing agent is added to that. Then, the mixture is heatedunder a nitrogen atmosphere and reacted. The organic solvent to be usedis not specifically limited. Examples thereof include toluene, xylene,ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutylketone, ethylene glycol monobutyl ether, diethylene glycol monobutylether, ethylene acetate glycol monoethyl ether and the like. Further,the radical polymerizing agent is not specifically limited. For example,cumene hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide,di-tert-butyl peroxide, benzoyl peroxide, acetyl peroxide, lauroylperoxide, azobisisobutyronitrile, hydrogen peroxide-Iron²⁺ salt,persulfate-NaHSO₃, cumene hydroperoxide-Iron²⁺ salt, benzoylperoxidedimethylaniline, peroxide-triethyl aluminum and the like areused. In order to control the molecular weight, a chain transfer agentcan be added. The chain transfer agent is not specifically limited.Examples thereof include quinones such as monoethyl hydroquinone orp-benzoquinone; thiols such as mercaptoacetic acid-ethyl ester,mercaptoacetic acid-n-butyl ester, mercaptoacetic acid-2-ethyl hexylester, mercaptocyclohexane, mercaptocyclopentane or 2-mercaptoethanol;thiophenols such as di-3-chlorobenzene thiol, p-toluene thiol or benzenethiol; thiol derivatives such as γ-mercaptopropyltrimethoxysilane;phenylpycrylhydrazine; diphenylamine; tert-butyl catechol, etc.

The formulation ratio of the photocatalyst (F) in the functional coatingmaterial (1) is not specifically limited because the photocatalyticperformance is exhibited regardless of the amount of the photocatalyst.For example, it is preferable to use 90 to 10 parts by weight, morefavorably, 50 to 10 parts by weight, based on 10 to 90 parts by weightof the resin solid content of the whole condensate of organosiloxane(E), provided that the total of the resin solid content of (E) and theamount of (F) comes to 100 parts by weight. If the amount of thephotocatalyst (F) is less than 10 parts by weight, sufficientphotocatalytic performance is not likely to be obtained. If it is morethan 90 parts by weight, the coating which is fragile and has nosmoothness tends to be obtained.

The formulation ratio of the photocatalyst (F) in the functional coatingmaterial (2) is not specifically limited because the photocatalyticperformance is exhibited regardless of the amount of the photocatalyst.For example, it is preferable to use 90 to 10 parts by weight, morefavorably, 50 to 10 parts by weight, based on 10 to 90 parts by weightof the resin solid content of the whole condensate of the total ofComponents (A) and (B), provided that the total of the resin solidcontent of Components (A) and (B) and the amount of (F) comes to 100parts by weight. If the amount of the photocatalyst (F) is less than 10parts by weight, there tends to be obtained no sufficient photocatalyticperformance. If it is more than 90 parts by weight, the coating which isfragile and has no smoothness tends to be obtained.

The formulation ratio of Components (A) and (B) in the functionalcoating material (2) is not specifically limited. For example,preferably, 99 to 1 parts by weight of component (B) is used with 1 to99 parts by weight of Component (A), more favor ably, 95 to 5 parts byweight of Component (B) is used with 5 to 95 parts by weight ofComponent (A), most favorably, 90 to 10 parts by weight of Component (B)is used with 10 to 90 parts by weight of Component (A) (provided thatthe total of Components (A) and (B) comes to 100 parts by weight). IfComponent (A) is less than 1 part by weight, the cold-curing propertiesare poor, or a coating having insufficient hardness is likely to beobtained. On the other hand, if Component (A) is more than 99 parts byweight, the curability of the coating is unstable, or there tends tooccur crack on the coating.

The formulation ratio of Component (C) in the functional coatingmaterial (2) is not specifically limited. For example, it is preferableto use 0.0001 to 10 parts by weight, more favorably 0.005 to 8 parts byweight, most favorably 0.007 to 5 parts by weight, based on 100 parts byweight of the total of the solid content of the whole condensate ofComponents (A) and (B). If Component (C) is less than 0.0001 parts byweight, the coating is not likely to be cured at a normal temperature.On the other hand, if it is more than 10 parts by weight, the heatresistance or weathering resistance of the cured coating tends to bedeteriorated.

The formulation ratio of Component (C) in the acryl-modified siliconeresin coating material is not specifically limited. For example, it ispreferable to use 0.001 to 10 parts by weight, more favorably, 0.005 to8 parts by weight, most favorably 0.007 to 5 parts by weight, based on100 parts by weight of the total of the solid content of the wholecondensate of Components (A), (B) and (C). If Component (C) is less than0.001 parts by weight, the coating is not likely to be cured at a normaltemperature. On the other hand, if it is more than 10 parts by weight,the heat resistance or weathering resistance of the cured coating tendsto be deteriorated.

The formulation ratio of Components (A), (B) and (D) in theacryl-modified silicone resin coating material is not specificallylimited. For example, when based on the solid content of the wholecondensate, preferably, 94 to 1 parts by weight of Component (B) and 5to 35 parts by weight of Component (D) are used with 1 to 94 parts byweight of Component (A), more favorably, 95 to 5 parts by weight ofComponent (B) and 5 to 35 parts by weight of Component (D) are used with5 to 95 parts by weight of Component (A), most favorably, 94 to 10 partsof Component (B) and 5 to 35 parts by weight of Component (D) are usedwith 10 to 94 parts by weight of Component (A) (provided that the totalof Components (A), (B) and (D) comes to 100 parts by weight). IfComponent (A) is less than 1 part by weight, the cold-curing propertiesare poor, or there tends to obtain no coating having sufficienthardness. On the other hand, if it is more than 94 parts by weight, thecuring properties are unstable or crack is liable to occur on thecoating. Further, if Component (D) is less than 5 parts by weight, theretends to be obtained no sufficient toughness or adhesion properties. IfComponent (D) is more than 35 parts by weight, there is high possibilitythat the deterioration of the coating may be accelerated due to thephotocatalyst in the upper layer.

In the functional coating material (1), a cured coating is formed by thecondensation reaction of hydrolytic groups contained in Component (E),by heating at a low temperature or by adding a curing catalyst andleaving them to stand at a normal temperature. Accordingly, thefunctional coating material (1) is hardly influenced by humidity even ifit is cured at a normal temperature. Further, if heat treatment isconducted, condensation reaction can be accelerated without using acuring catalyst and a cured coating can be formed.

In the functional coating material (2), a cured coating is formed by thecondensation reaction of a hydrolytic group in the organosilaneoligomer, which is contained in Component (A), with a silanol groupcontained in Component (B), in the presence of a curing catalyst (C), byleaving them to stand at a normal temperature or by heating at a lowtemperature. Accordingly, the functional coating material (2) is hardlyinfluenced by humidity even if it is cured at a normal temperature.Further, the condensation reaction is accelerated by heat treatment,thus, a cured coating can also be formed.

In the acryl-modified silicone resin coating material, a cured coatingis formed by the condensation reaction of a hydrolytic group in theorganosilane oligomer, which is contained in Component (A) and ahydrolytic group contained in acrylic resin (D) with a silanol groupcontained in Component (B), in the presence of a curing catalyst (C), byleaving them to stand at a normal temperature or by heating at a lowtemperature. Accordingly, the acryl-modified silicone resin coatingmaterial is hardly influenced by humidity even if it is cured at anormal temperature. Further, the condensation reaction is accelerated byheat treatment, thus, a cured coating can also be formed.

The acryl-modified silicone resin coating material may optionallycontain a pigment. The pigment to be used is not specifically limited.Examples thereof include organic pigments such as carbon black,quinacridone, naphthol red, Cyanine blue, Cyanine green or Ransa yellow;and inorganic pigments such as titanium oxide, barium sulfate, red oxideor composite metal oxide. One or two or more selected from the above mayalso be used in combination. The method for the dispersion of thepigment is not specifically limited, and it may be conducted by aconventional method, for example, by dispersing pigment powder directlyusing a Dyno mill, a paint shaker, etc. In that case, it is possible touse a dispersing agent, a dispersing additive, a thickening agent, acoupling agent and the like. The amount of the pigment to be added isnot specifically limited because the opacifying properties differdepending on the kind of the pigment. For example, it is preferable touse 5 to 80 parts by weight, more favorably 10 to 60 parts by weight,based on 100 parts by weight of the total of the solid content of thewhole condensate of Components (A), (B) and (D). If the amount of thepigment to be added is less than 5 parts by weight, the opacifyingproperties tend to be deteriorated. If it is more than 80 parts byweight, the smoothness of the coating may be deteriorated.

Further, a levelling agent, a dye, metal powder, glass powder, ananti-fungus agent, an anti-oxidizing agent, an antistatic agent, anultraviolet absorber and the like may be contained in an inorganiccoating material composition as long as they do not adversely affect theeffect of the prevent invention.

The respective functional coating materials (1), (2) and theacryl-modified silicone resin coating material may be optionally dilutedwith various organic solvents because of easy handling. Further, thedilute solution diluted with the above solvents may be used. The kind ofthe organic solvent can be suitably selected according to mono-valenthydrocarbon groups contained in Components (A), (B), (D) or (E), or tothe size of the molecular weight of Components (A), (B), (D) or (E).Such an organic solvent is not specifically limited. Examples thereofinclude lower aliphatic alcohols such as methanol, ethanol, isopropanol,n-butanol or isobutanol; ehtylene glycol derivatives such as ethyleneglycol, ethylene glycol monobutyl ether or ethylene acetate glycolmonoethyl ether; diethylene glycol derivatives such as diethylene glycolor diethylene glycol mono butyl ether; and toluene, xylene, hexane,heptane, ethyl acetate, butyl acetate, methyl ethyl ketone, methylisobutyl ketone, methyl ethyl ketoxime, diacetone alcohol, etc. One ortwo or more selected from the above can be used in combination. Thedilution ratio of the organic solvent is not specifically limited, andit may be suitably decided at need.

The method for applying the respective coating materials to thesubstrate is not specifically limited. For example, various conventionalcoating methods such as brushing, spraying, dipping, flow-coating, rollcoating, curtain coating, knife coating or spin coating can be selected.

The method for curing the respective coating materials, which areapplied to the substrate, is not specifically limited and it may beconducted by known methods. Further, the temperature when curing is notspecifically limited, and the temperature in the wide range between anormal temperature and a heated temperature can be taken, according tothe desired cured coating performance, whether the curing catalyst isused or not, and the heat resistance of the photocatalyst, etc.

The thickness of the cured coating formed from the functional coatingmaterials (1) or (2) is not specifically limited, because thephotocatalytic performance is exhibited regardless of its thickness. Forexample, the thickness of about 0.01 to 10 μm may be acceptable, but itis preferred that the thickness thereof is 0.05 to 5 μm, more favorably0.05 to 2 μm, in order to adhere and maintain the cured coating stablyfor a long period of time and also to prevent crack or peeling.

The thickness of the cured coating formed from the acryl-modifiedsilicone resin coating material is not specifically limited. Forexample, the thickness of about 0.1 to 100 μm may be acceptable, but itis preferred that the thickness thereof is 0.5 to 50 μm, in order torestrain deterioration of the substrate caused by the photocatalyst, toadhere and maintain the cured coating stably for a long period of timeand also to prevent crack or peeling.

The process for producing the functional coated product of the presentinvention is not specifically limited. For example, the process of thepresent invention is preferred.

The process of the present invention is conducted, for example, asfollows:

First, the acryl-modified silicone coating material is applied to thesurface of the substrate as the first, coating layer, and then the firstcoating layer is semi-cured. After that, the functional coating material(1) or (2) is applied to the surface of this semi-cured coating layer.That is, while the first coating layer is semi-cured, the functionalcoating material (1) or (2) is applied to that. At this time, if thefirst coating layer is completely cured before applying the functionalcoating material (1) or (2), the functional coating material (1) or (2)is peeled off due to the completely cured first coating layer, andtherefore a coating cannot be formed. Further, if the functional coatingmaterial (1) or (2) is applied while the first coating layer is stillwet, the first coating layer causes lifting (the adhesion propertiesbetween the first coating layer and the substrate cannot be obtained).

In the present specification “semi-curing” indicates “tack free drying”prescribed in JIS-K5400-1990. It means the condition such that noscratch is marked on the surface of the coating when the center of thecoating is gently rubbed with a fingertip. Further, “complete curing”indicates “hard drying” prescribed in JIS-K5400-1990. It means thecondition such that no depression due to a fingerprint is marked on thesurface of the coating and the movement of the coating is not felt, andalso no scratch is marked even when the center of the coating is rubbedfast with the fingertip repeatedly. Furthermore, “the coating layer isstill wet” means the condition such that the fingertip is stained whenthe center of the coating is gently touched with the fingertip.

As mentioned above, after the second coating layer is formed by applyingthe functional coating material (1) or (2) to the surface of thesemi-cured layer made of the acryl-modified silicone resin coatingmaterial, these semi-cured coating layer and second coating layer arecured.

Further, the process for obtaining the functional coated product of thepresent invention is not limited to the production process of thepresent invention.

The substrate to be used in the present invention is not specificallylimited. For example, when using a metallic substrate, an organicsubstrate and a substrate coated with an organic substance in whicheither one of the above substrates has a coating formed from an organicsubstance on the surface thereof, the effect of the improvement in theadhesion properties between the substrate and the coating or theprevention of the deterioration of the substrate is exhibited moreclearly. Therefore, the preferred is a substrate selected from the groupconsisting of a metallic substrate, an organic substrate and a substratecoated with an organic substance in which either one of the abovesubstrates has a coating formed from an organic compound on the surfacethereof. However, it should not be construed that the substrate islimited to them. For example, an inorganic substrate other than themetallic substrate and a substrate coated with an organic substancehaving a coating formed with an organic substance on the surface of theinorganic substrate other than the metallic substrate may also be used.

The inorganic substrate other than the metallic substrate is notspecifically limited. Examples thereof include a glass substrate,enamel, a water-glass ornamental plate, an inorganic constructionmaterial such as an inorganic cured material, ceramic and the like.

The metallic material is not specifically limited. Examples thereofinclude non-ferrous metal [e.g., aluminum (JIS-H4000, etc.), aluminumalloy (duralumin, etc.), copper, zinc, etc.], iron, steel [e.g., rolledsteel (JIS-G3101, etc.), hot-dip zinc-coated steel (JIS-G3302), (rolled)stainless steel (JIS-G4304, G4305, etc.), etc.], tinplate (JIS-G3303,etc.), and the whole range of other metal (including alloy).

The glass material is not specifically limited. Examples thereof includesodium soda glass, Pyrex glass, quartz glass, no-alkali glass and thelike.

The above-mentioned enamel is formed by coating the surface of the metalwith an enamel glass agent by means of baking. Examples of the substrateinclude, a mild steel plate, a steel plate, cast iron, aluminum and thelike. However, it is not limited to them. Concerning the enamel agent,conventional ones may be used and it is not specifically limited.

The above-mentioned water-glass ornamental plate indicates an ornamentalplate obtained, for example, by applying sodium silicate to a cementsubstrate such as slate, followed by baking.

The inorganic cured material is not specifically limited. Examplesthereof include the whole range of substrates obtained by cure-moldinginorganic materials such as a fiber reinforced cement plate (JIS-A5430,etc.), a ceramic siding (JIS-A5422, etc.), a cemented excelsior board(JIS-A5404, etc.), pulp cement flat sheet (JIS-A5414, etc.),slate/excelsior cemented laminated plate (JIS-A5426, etc.) a gypsumboard product (JIS-A6901, etc.), a clay roof tile (JIS-A5208, etc.), athick slate (JIS-A5402), a ceramic tile (JIS-A5209, etc.), a concreteblock for construction (JIS-A5406, etc.), terrazzo (JIS-A5411, etc.),prestressed concrete double T slab (JIS-A5412, etc.), an ALC panel(JIS-A5416, etc.), a hollow prestressed concrete panel (JIS-A6511, etc.)or a common brick (JIS-R1250, etc.).

The ceramic material is not specifically limited. Examples thereofinclude alumina, zirconia, silicon carbide, silicon nitride and thelike.

The organic substrate is not specifically limited. Examples thereofinclude plastic, wood, timber, paper and the like.

The plastic is not specifically limited. Examples thereof includethermosetting or thermoplastic plastics such as polycarbonate resin,acrylic resin, ABS resin, vinyl chloride resin, epoxy resin or phenolresin, and fiber reinforced plastic (FRP) obtained by reinforcing theabove plastics with glass fiber, nylon fiber, carbon fiber, etc.

The organic coating forming a substrate coated with an organic substanceis not specifically limited. Examples thereof include a cured coatingmade of a coating material containing organic resin such as acrylicresin, alkyd resin, polyester resin, epoxy resin, urethane resin,acrylsilicone resin, chlorinated rubber resin, phenolic resin ormelamine resin.

The form of the substrate is not specifically limited. Examples thereofinclude a film-shaped, sheet-shaped, plate-shaped, fiber-shapedsubstrate and the like. Further, the substrate may be a molded materialmade of the materials of these shapes or a compositional material a partof which has at least one of the molded materials of the above shapes orthe compositional materials.

The substrate may be formed from the above-mentioned various materialsalone, or it may be a composite material comprising at least two of theabove-mentioned various materials or a laminated material comprising thelamination of at least two of the above-mentioned various materials.

The functional coated product of the present invention can be suitablyused for the following use, by means of providing at least a part ofvarious materials or products, using various effects originating in theexcellent photocatalytic action.

A material or article related to building construction such as asheathing material (e.g., a material for outside wall, a roof tile suchas a flat roof tile, a clay roof tile or a metal roof tile), a rainwaterguttering such as a resin rainwater guttering (e.g., a PVC rainwaterguttering) or a metal rainwater guttering (e.g., a stainless steelrainwater guttering, etc.), a gate and a material to be used for that(e.g., a gate door leaf, a gate pier, a gate fence, etc.), a fence and amaterial to be used for that, a garage door leaf, a home terrace, adoor, a stanchion, a carport, a cycle port, a sign post, a deliverypost, a wiring apparatus such as a switchboard/switch, a gas meter, aninterphone, a main body and a camera lens portion of a video intercom,an electric lock, an entrance pole, a porch, an air outlet of aventilating fan or glass for building construction, a window (an openable window, e.g., a lighting window, a sky lighting, a louver, etc.)and a material to be used for that (e.g., a window frame, a weatherdoor, a blind, etc.) an automobile, a railway rolling stock, anaircraft, a marine structure, machine equipment, a material forhighway-related construction (e.g., a sound barrier, an interiormaterial for a tunnel, various display equipment, a guardrail, a carstop, a railing, a signboard and a signpost of a traffic-control sign, atraffic light, a post cone, etc.), a post for public notice, an outdooror indoor lighting fixture and a material to be used for that (e.g., aglass material, a resin material, a metallic material, a ceramicmaterial, etc.), glass for solar battery, agricultural-use vinyl sheetsand green house, an outdoor air conditioning unit, an antenna for VHF,UHF, BS, CS, etc.

Further, according to the present invention, the first coating layer andthe second coating layer may be directly formed on at least a part ofthe above-mentioned materials or articles. However, it is not limited tothem. For example, the functional coated product of the presentinvention wherein a base film material is used, namely, the functionalcoating comprising the first coating layer and the second coating layerformed on the surface of the base film material, may be pasted on atleast a part of various materials or articles. Examples of such a filmsubstrate include polyethylene terephthalate (PET) resin polybutylene-terephthalate (PBT) resin, PVC resin, acrylic resin, fluorineplastics, polypropylene (PP) resin, composite resin thereof and thelike, but it is not specifically limited.

EXAMPLES

The present invention is explained in detail by the following Examplesand Comparative Examples. It is, of course, not the intention hereby tolimit the invention. In Examples and Comparative Examples, “part”, “%”and “ppm” are all indicate “part by weight”, “% by weight” and “ppm byweight”, respectively, unless otherwise stated. Further, the measurementof the molecular weight was conducted by means of GPC (gel permeationchromatography) using a measuring apparatus, HLC8020 manufactured byToso Co., Ltd., to make a calibration curve with standard polystyrene.

EXAMPLES

First, functional coating materials (1), (2), acryl-modified siliconeresin coating materials and Comparative coating materials were prepared.

Preparation of a Functional Coating Material (1) and a ComparativeCoating Material

Preparation Example 1-1

Into a flask equipped with a stirrer, a warming jacket, a condenser, adropping funnel and a thermometer were charged 100 parts ofmethyltrimethoxysilane, 20 parts of tetraethoxysilane, 105 parts ofIPA-ST (colloidal silica sol dispersed in isopropanol: a particlediameter of 10 to 20 nm, a solid content of 30%, a water content of 0.5%manufactured by Nissan Kagaku Kogyo Co.), 30 parts ofdimethyldimethoxysilane, 100 parts of isopropanol. Thereafter, 100 ppmof hydrochloric acid based on the solid content of the whole condensate(30%) of this solution, and water of 3% on the basis of the abovesilicon alkoxide, were added to this solution mixture for hydrolysis at25° C. for 30 minutes while stirring the mixture. After cooling, thesilicone coating solution having an average molecular weight of about1,700 was obtained. To this were added 0.2 parts of lithium formate as acuring catalyst and titanium oxide as a photocatalyst (STS-01manufactured by Ishihara Sangyo Co., an average particle diameter of 7nm, a solid content of 30%) so that the weight ratio of the resin solidcontent of the silicone coating solution to the photocatalyst (resinsolid content/photocatalyst) was 80/20. Then, the mixture was dilutedwith methanol so that the whole solid content was 10% to give afunctional coating material (1-1).

Preparation Examples 1-2 to 1-5

Functional coating materials (1-2) to (1-5) were obtained in the samemanner as in Example 1, except that the amount of the photocatalystwhich was added was changed such that the resin solidcontent/photocatalyst weight ratio was 60/40, 50/50, 40/60 and 20/80,respectively. Further, the average molecular weight of theorganosiloxane was about 1,700 ((1-2) to (1-5)).

Comparative Preparation Example 1

The comparative functional coating material (1) was obtained in the samemanner as in Preparation Example 1, except that no photocatalyst wasused. The average molecular weight of the organosiloxane was about1,700.

Preparation of Functional Coating Material (2) and Comparative CoatingMaterial

Prior to the preparation of a coating material, Component (A) andComponent (B), which are to be used in the preparation, were prepared bythe following method.

Preparation Example A-1

Into a flask equipped with a stirrer, a warming jacket, a condenser anda thermometer were charged 100 parts of IPA-ST (colloidal silica soldispsesed in isoprppanol: a particle diameter of 10 to 20 nm, a solidcontent of 30%, a water content of 0.5% manufactured by Nissan KagakuKogyo Co.), 68 parts of methyltrimethoxysilane and 2.2 parts of waterwere charged. Then, the hydrolysis was conducted at 65° C. for 5 hourswhile stirring the mixture. After cooling, Companent (A-1) was obtained.The solid content of the whole condensate of this component was 37% whenit was left to stand at room temperature for 48 hours.

Conditions of the Preparation of A-1

The amount of water based on 1 mol of a hydrolytic groups (mol)₄0.1.

The amount of silica contained in Component (A-1) 47.3%

The amount of hydrolytic organosilane in which m=1 (mol %) 100 (mol %)

Preparation Example B-1

A solution in which 220 parts (1 mol) of methyltriisopropoxysilane wasdissolved in 150 parts of toluene was charged into a flask equipped witha stirrer, a warming jacket, a condenser, a dropping funnel and athermometer. To this was added dropwise 108 parts of a 1% solution ofhydrochloric acid over 20 minutes to conduct the hydrolysis ofmethyltriisopropoxysilane at 60° C. under stirring. Forty minutes afterthe completion of the dropping, the stirring was terminated. Thereaction mixture was poured from the flask into a separating funnel,followed by standing. Then, the reaction mixture was separated into twolayers. The mixed solution of water and isopropyl alcohol in theunderlayer, which contained hydrochloric acid in a small amount, wasremoved by separation. Then, hydrochloric acid remaining in the residualresin solution of toluene was removed by washing with water. Further,toluene was removed under reduced pressure. Thereafter, the residue wasdiluted with isopropyl alcohol to obtain a 40% isopropyl alcoholsolution of a silanol group-containing polyorganosiloxane having aweight-average molecular weight of about 2,000. This was used asComponent (B-1).

Preparation Example 2-1

Component (A-1) and Component (B-1) obtained above were mixed with thefollowing curing catalysts (C-1) and (C-2) in the following ratio. Tothis was added as a photocatalyst titanium oxide (manufactured byIshihara Sangyo Co. STS-02, an average particle diameter of 7 nm and asolid content of 30%) so that the weight ratio of the total resin solidcontent of Components (A-1) and (B-1) to the photocatalyst was 80/20.Thereafter, the mixture was diluted with methanol so that the totalsolid content was 10% to obtain a functional coating material (2-1).

Component (A-1): 50 parts (solid content: 18.5 parts) Component (B-1):50 parts (solid content: 20 parts) Component (C-1):N-β-aminoethyl-γ-aminopropylmethyl Dimethoxysilane: 2 parts Component(C-2): dibutiltin dilaurate 0.4 parts

Preparation Examples 2-2 to 2-5

The functional coating materials (2-2) to (2-5) were obtained in thesame manner as in Preparation Example 2-1, except that the amount of thephotocatalyst which was added was changed such that the resin solidcontent/photocatalyst weight ratio was 60/40, 50/50, 40/60 and 20/80,respectively.

Comparative Preparation Example (2)

The comparative coating material (2) was obtained in the same manner asin Preparation Example 2-1, except that no photocatalyst was used.

Preparation of Acryl-Modified Silicone Resin Coating Material andComparative Coating Material

Prior to the preparation of a coating material, Component (A), Component(B) and Component (D), which were to be used in the preparation, wereprepared by the following method.

Preparation Example A-2

Into a flask equipped with a stirrer, a warming jacket, a condenser anda thermometer were charged 100 parts of MA-ST (colloidal silica soldispersed in methanol: a particle diameter of 10 to 20 nm, a solidcontent of 30%, a water content of 0.5% manufactured by Nissan KagakuKogyo Co.), 68 parts of methyltrimethoxysilane, 49.5 parts ofphenyltrimethoxysilane, 16.0 parts of water and 0.1 parts of aceticanhydride. Then, the hydrolysis was conducted at 60° C. for 5 hourswhile stirring the mixture. After cooling, Companent (A-2) was obtained.The solid content of the whole condensate of this component was 41% whenit was allowed to stand for 48 hours at room temperature.

Conditions of the Preparation of A-2

-   -   The amount of water based on 1 mol of hydrolytic groups (mol):        0.4    -   The amount of silica contained in Component (A-2): 31.3%    -   The amount of hydrolytic organosilane in which m=1: 100 (mol %)

Preparation Example B-2

Into a flask equipped with a stirrer, a warming jacket, a condenser, adropping funnel and a thermometer were charged 1,000 parts of water and50 parts of acetone. Further, the hydrolysis was conducted while addingdropwise a solution, in which 44.8 parts (0.3 mol) ofmethyltrichlorosilane and 84.6 parts (0.4 mol) of phenyltrichlorosilanewere dissolved in 200 parts of toluene, to the mixture under stirring at60° C. Forty minutes after the completion of the dropping, the stirringwas terminated. The reaction mixture was poured from the flask into aseparating funnel, and then left to stand. Then, the reaction mixturewas separated into two layers. Aqueous hydrochloric acid in theunder-layer was removed by separation. Then, water and hydrochloric acidremaining in the toluene solution of the residual organopolysiloxane wasremoved together with the excess amount of toluene by means ofreduced-pressure stripping to obtain a 60% toluene solution of silanolgroup-containing polyorganosiloxane having a weight-average molecularweight of about 3,000. This was used as Component (B-2). It wasconfirmed that this silanol group-containing polyorganosiloxane inComponent (B-2) and Component (B-1) satisfied the above-mentionedaverage compositional formula

Preparation Example D-1

In a flask equipped with a stirrer, a warming jacket, a condenser, adropping funnel, a nitrogen-introducing/discharging opening and athermometer, a solution in which 0.025 parts (0.15 mmol) ofazobisisobutyronitrile was dissolved in 3 parts of toluene was addeddropwise to a reaction solution in which 5.69 parts (40 mmol) ofn-butylmethacrylate (BMA), 1.24 parts (5 mmol) oftrimethoxysilylpropylmethacrylate (SMA), 0.71 parts (5 mmol) of glycidylmethacrylate (GMA) and further 0.784 parts (4 mmol) ofγ-mercaptopropyltrimethoxysilane as a chain transfer agent weredissolved in 8.49 parts of toluene under a nitrogen atmosphere. Themixture was reacted at 70° C. for 2 hours. By this, a polymer having aweight-average molecular weight of 1,000 was obtained. This acrylicresin solution was used as Component (D-1) without any furthertreatment.

Conditions of the Preparation of D-1

The molar ratio of monomers BMA/SMA/GMA = 8.0/1.0/1.0 The weight-averagemolecular weight  1.000 The solid content 40% 

Preparation Example D-2

In a flask equipped with a stirrer, a warming jacket, a condenser, adropping funnel, a nitrogen-introducing/discharging opening and athermometer, a solution in which 0.025 parts (0.15 mmol) ofazobisisobutyronitrile was dissolved in 3 parts of toluene was addeddropwise to a reaction solution in which 0.71 parts (5 mmol) ofn-butylmethacrylate (BMA), 0.62 parts (2.5 mmol) oftrimethoxysilylpropylmethacrylate (SMA), 6.04 parts (42.5 mmol) ofglycidyl methacrylate (GMA) and further 0.196 parts (1 mmol) ofγ-mercaptopropyltrimethoxysilane as a chain transfer agent weredissolved in 8.06 parts of toluene under a nitrogen atmosphere. Themixture was reacted at 70° C. for 2 hours. By this, a polymer having aweight-average molecular weight of 3,000 was obtained. This acrylicresin solution was used as Component (D-2) without any furthertreatment.

Condition of the Preparation of D-2

The molar ratio of monomers BMA/SMA/GMA = 1.0/0.5/8.5 The weight-averagemolecular weight  3.000 The solid content 40% 

Preparation Example D-3

In a flask equipped with a stirrer, a- warming jacket, a condenser, adropping funnel, a nitrogen-introducing/discharging opening and athermometer, a solution in which 0.025 parts (0.15 mmol) ofazobisisobutyronitrile was dissolved in 3 parts of toluene was addeddropwise to a reaction solution in which 6.05 parts (42.5 mmol) ofn-butylmethacrylate (BMA), 0.62 parts (2.5 mmol) oftrimethoxysilylpropylmethacrylate (SMA), 0.71 parts (5 mmol) of glycidylmethacrylate (GMA) and further 0.098 parts (0.5 mmol) ofγ-mercaptopropyltrimethoxysilane as a chain transfer agent weredissolved in 8.06 parts of toluene under a nitrogen atmosphere. Themixture was reacted at 70° C. for 2 hours. By this, a polymer having aweight-average molecular weight of 5,000 was obtained. This acrylicresin solution was used as Component (D-3) without any furthertreatment.

Conditions of the Preparation of D-3

The molar ratio of monomers BMA/SMA/GMA = 8.5/6.5/1.0 The weight-averagemolecular weight  5.000 The solid content 40% Preparation Example D-4

In a flask equipped with a stirrer, a warming jacket, a condenser, adropping funnel, a nitrogen-introducing/discharging opening and athermometer, a solution in which 0.025 parts (0.15 mmol) ofazobisisobutyronitrile was dissolved in 3 parts of toluene was addeddropwise to a reaction solution in which 3.20 parts (22.5 mmol) ofn-butylmethacrylate (BMA), 1.24 parts (5 mmol) oftrimethoxysilylpropylmethacrylate (SMA), 3.20 parts (22.5 mmol) ofglycidyl methacrylate (GMA) and further 0.784 parts (4 mmol) ofγ-mercaptopropyltrimethoxysilane as a chain transfer agent weredissolved in 8.46 parts of toluene under a nitrogen atmosphere. Themixture was reacted at 70° C. for 2 hours. By this, a polymer having aweight-average molecular weight of 1,000 was obtained. This acrylicresin solution was used as Component (D-4) without any furthertreatment. Conditions of the preparation of D-4

The molar ratio of monomers BMA/SMA/GMA = 4.5/1.0/4.5 The weight-averagemolecular weight  1.000 The solid content 40% 

Preparation Example 3

Component (A-2), Component (B-2) and Component (D-1) obtained above weremixed with the following curing catalysts (C-1) and (C-2) in thefollowing ratio. Thereafter, the mixture was diluted with isopropylalcohol so that the solid content was 25% to obtain the functionalcoating material (1).

Component (A-2): 50 parts (solid content: 20.5 parts) Component (B-2):50 parts (solid content: 30 parts) Component (C-1):N-β-aminoethyl-γ-aminopropylmethyldimethoxy- silane 2 parts Component(C-2): dibutyltin dilaurate 0.4 parts Component (D-1): 20.25 parts(solid content: 8.1 parts)

Preparation Example 4

The acryl-modified silicone resin coating material (2) was obtained inthe same manner as in Preparation Example 3, except that the formulationratio of Components (A-2), (B-2), (C-1), (C-2) and (D-1) was changed asfollows.

-   Component (A-2): 50 parts (solid content: 20.5 parts)-   Component (B-2): 50 parts (solid content: 30 parts)-   Component (C-1): 2 parts-   Component (C-2): 0.4 parts-   Component (D-1): 6 parts (solid content: 2.4 parts)

Preparation Example 5

The acryl-modified silicone resin coating material (3) was obtained inthe same manner as in Preparation Example 3, except that the formulationratio of Components (A-2), (B-2), (C-1), (C-2) and (D-1) was changed asfollows.

-   Component (A-2): 50 parts (solid content: 20.5 parts)-   Component (B-2): 50 parts (solid content: 30 parts)-   Component (C-1): 2 parts-   Component (C-2): 0.4 parts-   Component (D-1): 53 parts (solid content: 20 parts)

Comparative Preparation Example 3

The comparative coating material (3) was obtained in the same manner asin Preparation Example 3, except that no Component (D-1) was used.

Preparation Example 6

The acryl-modified silicone resin coating material (4) was obtained inthe same manner as in Preparation Example 3, except that Components(A-2) and (B-2) were changed to Components (A-1) and (B-1),respectively, and that the formulation ratio of the respectivecomponents was as follows.

-   Component (A-1): 10 parts (solid content: 3.7 parts)-   Component (B-1): 10 parts (solid content: 4 parts)-   Component (C-1): 3 parts-   Component (C-2): 0.4 parts-   Component (D-1): 180 parts (solid content: 72 parts)

Preparation Example 7

The acryl-modified silicone resin coating material (5) was obtained inthe same manner as in Preparation Example 3, except that Components(A-2) and (B-2) were changed to Components (A-1) and (B-1),respectively, and that the formulation ratio of the respectivecomponents was as follows.

-   Component (A-1): 50 parts (solid content: 18.5 parts)-   Component (B-1): 50 parts (solid content: 20 parts)-   Component (C-1): 3 parts-   Component (C-2): 0.4 parts-   Component (D-1): 50 parts (solid content: 20 parts)

Preparation Example 8

The acryl-modified silicone resin coating material (6) was obtained inthe same manner as in Preparation Example 3, except that Components(A-2), (B-2) and (D-1) were changed to Components (A-1), (B-1) and(D-2), respectively, and that the formulation ratio of the respectivecomponents was as follows.

-   Component (A-1): 10 parts (solid content: 3.7 parts)-   Component (B-1): 10 parts (solid content: 4 parts)-   Component (C-1): 2 parts-   Component (C-2): 0.4 parts-   Component (D-2): 80 parts (solid content: 32 parts)

Preparation Example 9

The acryl-modified silicone resin coating material (7) was obtained inthe same manner as in Preparation Example 3, except that Components(A-2), (B-2) and (D-1) were changed into Components (A-1), (B-1) and(D-2), respectively, and that the formulation ratio of the respectivecomponents was as follows.

-   Component (A-1): 10 parts (solid content: 3.7 parts)-   Component (B-1): 10 parts (solid content: 4 parts)-   Component (C-1): 3 parts-   Component (C-2): 0.4 parts-   Component (D-2): 180 parts (solid content: 72 parts)

Preparation Example 10

The acryl-modified silicone resin coating material (8) was obtained inthe same manner as in Preparation Example 3, except that Components(A-2), (B-2) and (D-1) were changed to Components (A-1), (B-1) and(D-3), respectively, and that the formulation ratio of the respectivecomponents was as follows.

-   Component (A-1): 10 parts (solid content: 3.7 parts)-   Component (B-1): 10 parts (solid content: 4 parts)-   Component (C-1): 3 parts-   Component (C-2): 0.4 parts-   Component (D-3): 180 parts (solid content: 72 parts)

Preparation Example 11

The acryl-modified silicone resin coating material (9) was obtained inthe same manner as in Preparation Example 3, except that Components(A-2), (B-2) and (D-1) were changed to Components (A-1), (B-1) and(D-4), respectively, and that the formulation ratio of the respectivecomponents was as follows.

-   Component (A-1): 10 parts (solid content: 3.7 parts)-   Component (B-1): 10 parts (solid content: 4 parts)-   Component (C-1): 3 parts-   Component (C-2): 0.4 parts-   Component (D-4): 180 parts (solid content: 72 parts)

Examples 1 to 10 and Comparative Examples 1 and 2

Using a PC (polycarbonate) plate (50 mm×50 mm×2.5 mm) as a substrate,the first applied layer was formed by means of spray coating with theacryl-modified silicone resin coating material (1) prepared inPreparation Example 3 so that the cured coating thickness was 1 μm.Then, the coating was cured at 60° C. for 15 minutes. After that, thesetting time was provided for 10 minutes. After the completion of thesetting time, the center of the coated surface was strongly pinched witha thumb and an index finger to form depressions on the coated surfacedue to a fingerprint. Also, the movement of the coating was felt.However, even if the center of the coating was gently rubbed with afingertip, no scratch was formed on the coated surface. From thisresults, it was confirmed that the first coating layer-was a semi-curedcondition.

The second coating layer was formed by means of spray coating with thefunctional coating materials (1-1) to (1-5), (2-1) to (2-5) orcomparative coating materials (1) and (2) so that the cured coatingthickness was 0.5 μm. After that, the second coating layer was allowedto stand at room temperature for one week to obtain functional coatedproducts (1) to (10) and a comparative coated products (1) and (2).

Concerning the functional coated products (1) to (10) and comparativecoated products (1) and (2), tests for coating properties and forpreventive properties for deterioration were conducted by the followingevaluation method.

Evaluation on Coating Properties

Adhesion Properties

Adhesion properties to the substrate were evaluated by the peeling testusing adhesive tape having a pattern of squares (cellophane tape wasused).

Surface Hardness

It was conducted according to hardness test using a pencil (based onJIS-K5400).

Photocatalytic Action

Into a 300 ml container containing a sample, 50 ppm of acetaldehyde wasinjected. Black light (10 W) was irradiated to the container for 60minutes to measure the ratio of the removed aldehyde (%) by means of gaschromatography (GC14A manufactured by Shimazu Seisakusho K.K.).

Wettability to Water

It was evaluated by measuring the contact angle formed by water and thecoating. The contact angle was measured when the coating was in theinitial stage after preparation, and after the coating was irradiated byUV light for 24 hours using an UV-irradiation device (HANDY UV300manufactured by OAK FACTORY).

Evaluation on the Deterioration of a Substrate and a Coating

Light was irradiated with a Sunshine Weatherometer (according toJIS-K5400) for 2,500 hours to observe a substrate and a coating. Thosewhich showed no change were evaluated to be good.

Evaluation results were shown in Tables 1 and 2. As shown in thesetables, in the second coating layer, the more the content of titaniumoxide, which was used as a photocatalyst, the better photocatalyticperformance was exhibited. However, the hardness is somewhatdeteriorated if the ratio of titanium oxide is 80% or more. Further, theadhesion properties between the substrate and the first coating layer,those between the first coating layer and the second coating layer weregood. Further, concerning the functional coated products (1) to (10),sufficient photocatalytic performance was exhibited although the secondcoating layer containing the photocatalyst was cured at roomtemperature. Concerning wettability of the coating, after theirradiation of UV light, every functional coated product had a contactangle of a few degree regardless of the amount of the photocatalystcontained in the coating layer, which showed high wettability.Furthermore, concerning the functional coated products (1) to (10)having a coating layer containing the photocatalyst, although a PCplate, which is easily subjected to the deterioration due to thephotocatalyst, was used, the deterioration of the substrate wassufficiently prevented by interposing a coating layer made of theacryl-modified silicone resin coating material between the coatingcontaining the photocatalyst and the substrate. Further, thedeterioration of the coating was not observed, either.

Comparative Example 3

A comparative coated product (3) was obtained in the same manner as inExample 1, except that the second coating layer was formed only withtitanium oxide instead of forming a cured coating of the functionalcoating material.

Concerning the comparative coated product (3), the evaluation on coatingproperties and deterioration of the substrate and the coating wereconducted according to the above-mentioned method.

The results thereof were shown in Table 3. As shown in this table,photocatalytic performance was very good, however, the coating of thesecond coating layer was fragile because the second coating layercomprises sol only. Therefore, the first coating layer and the secondcoating layer were not adhered. Also, it was not easy to measure thehardness. Concerning the deterioration of the substrate, yellowing wasseen on the PC plate.

Comparative Example 4

A comparative coated product (4) was obtained in the same manner as inExample 3, except that the first coating layer was formed with a curedcoating made of a comparative coating material (3) containing noComponent (D), instead of forming a cured coating made of theacryl-modified silicone resin coating material (1).

Concerning the comparative coated product (4), the evaluation on coatingproperties and deterioration of the substrate and the coating wereconducted according to the above-mentioned method.

The results thereof were shown in Table 3. As shown in this table,adhesion properties between the substrate and the first coating layerwere not obtained. There was no problems concerning the deterioration ofthe substrate and the coating.

Comparative Example 5

A comparative coated product (5) was obtained in the same manner as inExample 3, except that the functional coating material (1-3) wasdirectly applied to the surface of the substrate without using theacryl-modified silicone resin coating material and that the curing wasconducted.

Concerning the comparative coated product (5), the evaluation on coatingproperties and deterioration of the substrate and the coating wereconducted according to the above-mentioned method.

The results thereof were shown in Table 3. As shown in this table,adhesion properties between the substrate and the cured coating of thefunctional coating material were not obtained. Further, the substratewas deteriorated due to the action of the photocatalyst contained in thecured coating of the functional coating material.

Comparative Example 6

A comparative coated product (6) was obtained in the same manner as inComparative Example 1, except that the comparative functional coatingmaterial (1) was directly applied to the surface of the substratewithout using the acryl-modified silicone resin coating material andthat the curing was conducted.

Concerning the comparative coated product (6), the evaluation on coatingproperties and deterioration of the substrate and the coating wereconducted according to the above-mentioned method.

The results thereof were shown in Table 3. As shown in this table, thedeterioration of the substrate and the coating was not observed,however, adhesion properties between the substrate and the cured coatingformed with the coating material were not obtained.

Examples 11 to 13 Examples of Colored Coating

Functional coated products (11) to (1.3) were obtained in the samemanner as in Example 3, except that the first coating layer was formedwith enamel obtained by adding the following pigments (1) to (3) to theacryl-modified silicone resin coating material (1), instead of theacryl-modified silicone resin coating material (1) which was used forforming the first coating layer.

-   -   Pigment 1: White pigment (manufactured by Ishihara Sangyo Co.,        Ltd.) P.W.C.40    -   Pigment 2: Yellow pigment (manufactured by Dainichi Seika Co.,        Ltd.) P.W.C.40    -   Pigment 3: Black pigment (manufactured by Dainichi Seika Co.,        Ltd.) P.W.C.40    -   P.W.C.: Pigment Weight Concentration (Weight % in the solid        content)

Examples 14 to 16 Examples of Colored Coating

Functional coated products (14) to (16) were obtained in the same manneras in Example 8, except that the first coating layer was formed withenamel obtained by adding the above-mentioned pigments (1) to (3) to theacryl-modified silicone resin coating material (1), instead of theacryl-modified silicone resin coating material (1) which was used forforming the first coating layer.

Concerning the functional coated products (11) to (16), the evaluationon coating properties and deterioration of the substrate and the coatingwere conducted according to the above-mentioned method.

The results thereof were shown in Table 4. As shown in this table, therewas no problem concerning the coating properties and the deteriorationof the substrate and the coating, even if the first coating layer wascoated by means of enamel coating.

Example 17

A functional coated product (17) was obtained in the same manner as inExample 3, except that the thickness of the cured coating of the secondcoating layer was changed to 0.1 μm.

Example 18

A functional coated product (18) was obtained in the same manner as inExample 8, except that the thickness of the cured coating of the secondcoating layer was changed to 0.1 μm.

Comparative Example 7

A comparative coated product (7) was obtained in the same manner as inComparative Example 1, except that the thickness of the second coatinglayer was changed to 0.1 μm.

Concerning the functional coated products (17), (18) and comparativecoated product (7), the evaluation on coating properties anddeterioration of the substrate and the coating were conducted accordingto the above-mentioned method.

The results thereof were shown in Table 5. As shown in this table, thecured coating of the functional coating material containing thephotocatalyst of the functional coated products (17) and (18) had acontact angle of a few degrees, after the irradiation of ultravioletlight to show high wettability, in spite of a small layer thickness. Onthe other hand, the coating of Comparative coated product (7), in whicha silicone coating material containing no photocatalyst was used, didnot show this performance.

Example 19

A functional coated product (19) was obtained in the same manner as inExample 3, except that the acryl-modified silicone resin coatingmaterial (2), which was obtained in Preparation Example 4, was usedinstead of the acryl-modified silicone coating resin material (1).

Example 20

A functional coated product (20) was obtained in the same manner as inExample 3, except that the acryl-modified silicone resin coatingmaterial (3), which was obtained in Preparation Example 5, was usedinstead of the acryl-modified silicone coating resin material (1).

Concerning the functional coated products (19) and (20), the evaluationon coating properties and deterioration of the substrate and the coatingwere conducted according to the above-mentioned method.

The results thereof were shown in Table 6. As shown in this table, therewas no problem concerning adhesion properties between the substrate andthe first coating layer end those between the first coating layer andthe second coating layer. There was no problem concerning otherperformance, either.

Example 21

A functional coated product (21) was obtained in the same manner as inExample 3, except that a PVC plate having the same size as that of thePC plate was used as a substrate.

Example 22

A functional coated product (22) was obtained in the same manner as inExample 8, except that a PVC plate having the same size as that of thePC plate was used as a substrate.

Comparative Example 8

A comparative coated product (8) was obtained in the same manner as inExample 3, except that a PVC plate having the same size as that of thePC plate was used as a substrate and that the functional coatingmaterial (1-3) was directly applied to the surface of this PVC platewithout using the acryl-modified silicone resin coating material.

Example 23

A functional coated product (23) was obtained in the same manner as inExample 3, except that a plate coated with an organic substance havingthe same size as that of the PC plate (in which an acrylic coatingPERMALOCK (manufactured by Rock Paint Co.) was applied in a thickness of10 μm to an inorganic substrate made of a stainless steel plate) wasused as a substrate.

Example 24

A functional coated product (24) was obtained in the same manner as inExample 8, except that a plate coated with an organic substance havingthe same size as that of the PC plate (in which an acryl coatingPERMALOCK (manufactured by Rock Paint Co.) was applied in a thickness of10 μm to an inorganic substrate made of a stainless steel plate) wasused as a substrate.

Comparative Example 9

A comparative coated product (9) was obtained in the same manner as inExample 3, except that a plate coated with an organic substance havingthe same size as that of the PC plate (in which an acrylic coatingPERMALOCK (manufactured by Rock Paint Co.) was applied in a thickness of10 μm to an inorganic substrate made of a stainless steel plate) wasused as a substrate and that the functional coating material (1-3) wasdirectly applied to the surface of this plate coated with the organicsubstance and curing was conducted.

Concerning the functional coated products (21) to (24) and comparativecoated products (8) and (9), the evaluation on coating properties anddeterioration of the substrate and the coating were conducted accordingto the above-mentioned method.

The results thereof were shown in Table 7. As shown in this table, thefunctional coated products (21) to (24) in Examples, in which the firstcoating layer was formed with the cured coating of the acryl-modifiedcoating material, showed no problem in adhesion properties, and thedeterioration of the substrate and the coating was not observed. Also,other performance was good. On the other hand, the coparative coatedproducts (8) and (9) in Comparative Examples showed poor adhesionproperties, further, the deterioration of the substrate due to thephotocatalyst was observed.

Example 25

A functional coated product (25) was obtained in the same manner as inExample 3, except that a stainless steel plate having the same size asthat of the PC plate was used as a substrate.

Example 26

A functional coated product (26) was obtained in the same manner as inExample 8, except that a stainless steel plate having the same size asthat of the PC plate was used as a substrate.

Comparative Example 10

A comparative coated product (10) was obtained in the same manner as inExample 3, except that a stainless steel plate having the same size asthat of the PC plate was used as a substrate and that the functionalcoating material (1-3) was directly applied to the surface of thisstainless steel plate without applying the acryl-modified silicone resincoating material and the curing was conducted.

Concerning the functional coated products (25) and (26) and Comparativecoated product (10), the evaluation on coating properties anddeterioration of the substrate and the coating were conducted accordingto the above-mentioned method.

The results thereof were shown in Table 8. As shown in this table, therewas no problem concerning the deterioration of the substrate because aninorganic substrate was used in every coated product. However, thecomparative coated product (10) was poor in adhesion properties, becausethe first coating layer made of a cured coating of the acryl-modifiedsilicone resin coating material was not formed.

Example 27

A functional coated product (27) was obtained in the same manner as inExample 3, except that a glass plate having the same size as that of thePC plate was used as a substrate.

Example 28

A functional coated product (28) was obtained in the same manner as inExample 8, except that a glass plate having the same size as that of thePC plate was used as a substrate.

Example 29

A functional coated product (29) was obtained in the same manner as inExample 3, except that a tile having the same size as that of the PCplate was used as a substrate.

Example 30

A functional coated product (30) was obtained in the same manner as inExample 8, except that a tile having the same size as that of the PCplate was used as a substrate.

Example 31

A functional coated product (31) was obtained in the same manner as inExample 3, except that an enamel plate having the same size as that ofthe PC plate was used as a substrate.

Example 32

A functional coated product (32) was obtained in the same manner as inExample 8, except that an enamel plate having the same size as that ofthe PC plate was used as a substrate.

Concerning the functional coated products (27) to (32), the evaluationon coating properties and deterioration of the substrate and the coatingwere conducted according to the above-mentioned method.

The results thereof were shown in Tables 8 and 9. As shown in thesetables, there was no problem concerning the deterioration of thesubstrate because an inorganic substrate was used in every coatedproduct. Also, there was no problem concerning other performance.

Comparative Example 11

A comparative coated product (11) was obtained in the same manner as inExample 3, except that the acryl-modified silicone resin coatingmaterial (1), which was applied to the surface of the PC plate, wasbaked at 150° C. for 30 minutes to conduct complete curing (the ratio ofthe cured acryl-modified silicone resin coating material was 100% byweight, which was obtained in the same manner as in Example 3), and thenthe functional coating material (1-3) was applied to the surfacethereof.

However, the coating of the functional coating material (1-3) could notbe formed because the functional coating material (1-3) on thecompletely cured layer was repelled.

Comparative Example 12

A comparative coated product (12) was obtained in the same manner as inExample 3, except that the acryl-modified silicone resin coatingmaterial (1), which was applied to the surface of the PC plate, was leftto stand for 10 minutes at room temperature and then the functionalcoating material (1-3) was applied to the surface thereof, while theapplied acryl-modified silicone resin coating material (1) was in a wetcondition.

Concerning the comparative functional coated product (12), theevaluation on coating properties and deterioration of the substrate andthe coating were conducted according to the above-mentioned method.

The results thereof were shown in Table 10. As shown in this table,sufficient adhesion properties were not obtained between the substrateand the first coating layer.

Examples 33 to 37

Functional coated products (33) to (37) were obtained in the same manneras in Example 3, except that a tile having the same size as that of thePC plate was used as a substrate and that the first coating layer wasformed with acryl-modified silicone resin coating materials (4) to (8)instead of the acryl-modified silicone resin coating material (1).

Example 38

A functional coated product (38) was obtained in the same manner as inExample 8, except that a tile having the same size as that of the PCplate was used as a substrate and that the first coating layer wasformed with an acryl-modified silicone resin coating material (9)instead of the acryl-modified silicone resin coating material (1).

Comparative Example 13

A comparative coated product (13) was obtained in the same manner as inExample 8, except that a tile having the same size as that of the PCplate was used as a substrate, that the first coating layer was formedwith a commercially available epoxy-type primer (EPORO Z PRIMER,manufactured by ISAMU PAINT CO.) instead of the acryl-modified siliconeresin coating material (1), and that the thickness of the cured coatingof the first coating layer was changed to 8 μm.

Comparative Example 14

A comparative coated product (14) was obtained in the same manner as inExample 8, except that a tile having the same size as that of the PCplate was used as a substrate, that the first coating layer was formedwith an acryl-modified silicone resin coating material (7) instead ofthe acryl-modified silicone resin coating material (1), and that thesecond coating layer was formed with the comparative coating material(1) instead of the functional coating material (2-3).

In order to study the durability of the coating and the influence on thefirst coating layer due to the photocatalytic ability, the followingaccelerated weathering evaluation was conducted with the above-mentionedSunshine Weatherometer, as for the functional coated products (29),(30), (33) to (38) and comparative coated products (13) and (14).Further, the reason why the tile was used as a substrate of the coatedproduct was because the tile has less weathering deterioration.Therefore, it is possible to examine the durability of the coatingitself clearly.

The test time was 4,000 hours, and the adhesion properties and degree ofdiscoloration of the coating was examined. Further, the adhesionproperties and degree of discoloration of the coating was also examinedhalfway, 2,500 hours after the test.

The adhesion properties were examined according to the above-mentionedmethod.

The degree of discoloration was conducted according to the colordifference (ΔE) prescribed in JIS-Z8730. In general, it is said that aperson's eye can confirm the discoloration when ΔE is 3 or more.Further, it is said that the irradiation for 4,000 hours by the SunshineWeatherometer corresponds to exposure outdoors for 10 years.

Evaluation results are shown in Tables 11 and 12.

As shown in Tables 11 and 12, concerning the functional coated products(29), (30) and (33) to (38), the discoloration was more serious,particularly after 4,000 hours, when the ratio of Component (D) wasincreased. However, it does not seem to cause any problems on thepractical use, except for the case where high durability is required.Particularly, in the functional coated product (36) in Example 36, pooradhesion occurred in some parts between the first coating layer and thesecond coating layer 4,000 hours later. However, the deterioration wasnot observed 2,500 hours later.

Further, the comparative coated product (13), in which the commerciallyavailable epoxy-type primer was used, showed remarkable deterioration inthe coating performance. Concerning the coated product in ComparativeExample 14, the degree of discoloration of the coating was reducedthough the first coating layer was formed from the same material as thatof the functional coated product (36) in Example 36, because thephotocatalyst was not contained in the second coating layer.

Example 39

EPORO E PRIMER (manufactured by ISAMU PAINT, CO.) was applied to about 5m² of a concrete side wall (no coated) of a path in the premise of thehead office of Matsushita Electric Works, Ltd. (Kadoma, Osaka) as aprime coat, in order to prevent the elution of an alkaline component inthe concrete, under predetermined conditions. After drying for 24 hours,colored coating was conducted with the pigment-containing acryl-modifiedsilicone resin coating material prepared in Example 11, so that thethickness of the cured coating was about 30 μm. After it was left tostand for 5 hours at room temperature, it was confirmed that the curedcoating was a semi-cured condition. Then, the functional coatingmaterial (2-3) prepared in Preparation Example 2-3 was applied theretoso that the thickness of the cured coating was about 0.5 μm. All thecoating was conducted using a hand roller.

After exposure for about 3 months, there was no dirt on the coated sidewall and it maintained the condition in the beginning of the coating.

Example 40

An acryl-modified coating material (1) prepared in Preparation Example 3was applied to a road traffic sign ((width) 600 mm×(length) 350 mm, anone-way sign) and a pole in the premise of the head office of MatsushitaElectric Works, Ltd. (Kadoma, Osaka), after wiping off the dirt withethanol, so that the thickness of the cured coating was about 5 μm.After it was left to stand for 5 hours at room temperature, it wasconfirmed that the cured coating was a semi-cured condition. Then, thefunctional coating material (1-3) prepared in Preparation Example 1-3was applied thereto so that the thickness of the cured coating was about0.5 μm. All the coating was conducted by means of brushing.

After exposure for about 3 months, there was no dirt on the coated sidewall and it maintained the condition in the beginning of the coating.

Example 41

The first coating layer and the second coating layer were formed on areflective tape for a road traffic sign (manufactured by Sumitomo 3MCo.) and on a post cone for a road (manufactured by Nippon Mectron Co.)in the same manner as in Example 3. The reflective tape was pasted onthe post cone, followed by exposure for about 3 months at the side ofthe road in the premise of the head office of Matsushita Electric Works,Ltd. (Kadoma, Osaka). There was no dirt on the post cone and itmaintained the condition in the beginning of the coating.

Example 42

The acryl-modified silicone resin coating material (1) prepared inExample 3 was applied to an outer wall (about 10 m²) of the mainbuilding in the premise of the head office of Matsushita Electric Works,Ltd. (Kadoma, Osaka), so that the thickness of the cured coating wasabout 8 μm. After it was left to stand for 4 hours at room temperature,it was confirmed that the cured coating was a semi-cured condition.Then, the functional coating material (1-3) prepared in PreparationExample 1-3 was applied thereto so that the thickness of the curedcoating was about 0.5 μm. All the coating was conducted using a handroller. After exposure for about 3 months, there was no dirt on thecoated building and it maintained the condition in the beginning of thecoating.

Example 43

The acryl-modified coating material (1) prepared in Preparation Example3 was applied to a glass having a size of 1 m² (a thickness of 6 mm) ofthe research laboratory (east side, the second floor) in the premise ofthe head office of Matsushita Electric Works, Ltd., after wiping off thedirt with ethanol, so that the thickness of the cured coating was about1 μm. After it was left to stand for 2 hours at room temperature, it wasconfirmed that the cured coating was a semi-cured condition. Then, thefunctional coating material (2-3) prepared in Preparation Example 2-3was applied thereto so that the thickness of the cured coating was about0.5 μm. All the coating was conducted by means of flow coating.

After exposure for about 3 months, there was no dirt on the coatedbuilding and it maintained the condition in the beginning of thecoating.

Example 44

The acryl-modified coating material (1) prepared in Preparation Example3 was applied to the whole apparatus of the road light (YA32020 forsidewalk, manufactured by Matsushita Electric Works, Ltd.) includingfront glass, a pole, an outer surface of a reflective plate, etc., inthe premise of the head office of Matsushita Electric Works, Ltd., afterwiping off the dirt with ethanol, so that the thickness of the curedcoating was about 1 μm. After it was left to stand for 2 hours at roomtemperature, it was confirmed that the cured coating was a semi-curedcondition. Then, the functional coating material (1-3) prepared inPreparation Example 1-3 was applied thereto so that the thickness of thecured coating was about 0.5 μm. All the coating was conducted with asponge roller.

After exposure for about 3 months, there was no dirt on the coated frontglass, the pole, the reflective plate, etc. and it maintained thecondition in the beginning of the coating.

Example 45

The acryl-modified coating material (1) prepared in Preparation Example3 was applied to an auto body (TOFOTA SPRINTER, the 1990 model), afterwiping off the dirt with ethanol, so that the thickness of the curedcoating was about 1 μm. After it was left to stand for 2 hours at roomtemperature, it was confirmed that the cured coating was a semi-curedcondition. Then, the functional coating material (1-3) prepared inPreparation Example 1-3 was applied thereto so that the thickness of thecured coating was about 0.5 μm. All the coating was conducted with asponge roller.

After exposure for about 3 months, there was no dirt on the coated autobody and it maintained the condition in the beginning of the coating.

Example 46

EPORO E PRIMER (manufactured by ISAMU PAINT, CO.) was applied to acement-type facing material (manufactured by Matsushita Electric Works,Ltd., a multi-sizing brick tile pattern) as a prime coat, in order toprevent the elution of an alkaline component, under predeterminedconditions. After drying for 24 hours, colored coating was conductedwith the pigment-containing acryl-modified silicone resin coatingmaterial prepared in Example 11, so that the thickness of the curedcoating was about 30 μm. After it was left to stand for 5 hours at roomtemperature, it was confirmed that the cured coating was a semi-curedcondition. Then, the functional coating material (2-3) prepared inPreparation Example 2-3 was applied thereto so that the thickness of thecured coating was about 0.5 μm. All the coating was conducted by meansof airless spray.

After exposure for about 3 months, there was no dirt on the facingmaterial and it maintained the condition in the beginning of thecoating.

Example 47

Half of the area of a reflective plate (a steel plate coated with whitemelamine) for a Fuji-type fluorescent lighting apparatus (20W), (FA22063manufactured by Matsushita Electric Works, Ltd.), was applied in thesame manner as in Example 3, except that the second coating layer wasdried at 90° C. for 15 minutes. All the coating was conducted by meansof airless spray. The fluorescent lighting apparatus, including thereflective plate coated in that way, was equipped in the cookery of theinternal cafeteria in the premise of the head office of MatsushitaElectric Works, Ltd. (Kadoma, Osaka), and it was observed. About threemonths later, the coated portion had less dirt compared with the otherportion.

Example 48

EPORO E PRIMER (manufactured by ISAMU PAINT, CO.) was applied to about 1m² of a concrete electric-light pole (no coated) in the premise of thehead office of Matsushita Electric Works, Ltd. (Kadoma, Osaka) as aprime coat, in order to prevent the elution of an alkaline component inthe concrete, under predetermined conditions. After drying for 24 hours,colored coating was conducted with the pigment-containing acryl-modifiedsilicone resin coating material prepared in Example 11, so that thethickness of the cured coating was about 30 μm. After it was left tostand for 5 hours at room temperature, it was confirmed that the curedcoating was a semi-cured condition. Then, the functional coatingmaterial (1-3) prepared in Preparation Example (1-3) was appliedthereto, so that the thickness of the cured coating was about 0.5 μm.All the coating was conducted using a hand roller.

After exposure for about 3 months, there was no dirt on the coatedelectric-light pole and it maintained the condition in the beginning ofthe coating.

Example 49

The acryl-modified silicone resin coating material (1) prepared inpreparation Example 3 was applied to a protection fence (a galvanizedsteel plate) in the premise of the head office of Matsushita ElectricWorks, Ltd. (Kadoma, Osaka), after wiping off the dirt with ethanol, sothat the thickness of the cured coating was about 1 μm. After it wasleft to stand for one hour at room temperature, it was confirmed thatthe cured coating was a semi-cured condition. Then, the functionalcoating material (1-3) prepared in Preparation Example (1-3) was appliedthereto, so that the thickness of the cured coating was about 0.5 μm.All the coating was conducted using a hand roller.

After exposure for about 3 months, there was no dirt on the coatedprotection fence and it maintained the condition in the beginning of thecoating.

TABLE 1 Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 1 Coated productFunc.*¹(1) Func. (2) Func. (3) Func. (4) Func. (5) Comp.*² (1) SubstratePC plate PC plate PC plate PC plate PC plate PC plate First coatinglayer Coating Acryl- Acryl- Acryl- Acryl- Acryl- Acryl- materialModified modified modified modified modified modified Silicone siliconesilicone silicone silicone silicone Resin (1) resin (1) resin (1) resin(1) resin (1) resin (1) Coating 1 1 1 1 1 1 thickness (μm) Secondcoating layer Coating Func. Func. Func. Func. Func. Comp. material (1-1)(1-2) (1-3) (1-4) (1-5) (1) Resin solid content/ 80/20 60/40 50/50 40/6020/80 100/0 photocatalyst (weight ratio) Coating Thickness (μm) 0.5 0.50.5 0.5 0.5 0.5 Photocatalytic action 10 40 47 56 79 0 Adhesionproperties Between substrate and 100/100 100/100 100/100 100/100 100/100100/100 first coating layer Between first coating 100/100 100/100100/100 100/100 100/100 100/100 layer and second coating layer HardnessContact Angle 5 H 4 H 4 H 3 H 2 H 6 H Initial stage 75° 73° 72° 60° 50°75° After UV irradiation <10° <10° <10° <10° <10° 75° Deterioration ofcoating None None None None None None Deterioration of substrate NoneNone None None None None *¹Func.: Functional (same below) *²Comp.:Comparative (same below)

TABLE 2 Comp. Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 2 Coated product Func.(6) Func. (7) Func. (8) Func. (9) Func. (10) Comp. (2) Substrate PCplate PC plate PC plate PC plate PC plate PC plate First coating layerCoating Acryl- Acryl- Acryl- Acryl- Acryl- Acryl- material modifiedmodified modified modified modified modified silicone silicone siliconesilicone silicone silicone resin (1) resin (1) resin (1) resin (1) resin(1) resin (1) Coating 1 1 1 1 1 1 thickness (μm) Second coating layerCoating Func. Func. Func. Func. Func. Comp. material (2-1) (2-2) (2-3)(2-4) (2-5) (2) Resin solid content/ 80/20 60/40 50/50 40/60 20/80 100/0photocatalyst (weight ratio) Coating thickness (μm) 0.5 0.5 0.5 0.5 0.50.5 Photocatalytic action 8 36 44 55 72 0 Adhesion properties Betweensubstrate and 100/100 100/100 100/100 100/100 100/100 100/100 firstcoating layer Between first coating 100/100 100/100 100/100 100/100100/100 100/100 layer and second coating layer Hardness Contact Angle 4H 4 H 4 H 3 H 2 H 5 H Initial stage 80° 78° 78° 74° 65° 80° After UVirradiation <10° <10° <10° <10° <10° 80° Deterioration of coating NoneNone None None None None Deterioration of substrate None None None NoneNone None

TABLE 3 Comp. Comp. Comp. Comp. Ex. 3 Ex. 4 Ex. 5 Ex. 6 Coated productComp. (3) Comp. (4) Comp. (5) Comp. (6) Substrate PC plate PC plate PCplate PC plate First coating layer Coating Acryl- Comp. (3) — — materialmodified silicone resin (1) Coating 1 1 — — thickness (μm) Secondcoating layer Coating Titanium Func. Func. Comp. material oxide (1-3)(1-3) (1) Resin solid content/ — 50/50 50/50 100/0  photocatalyst(weight ratio) Coating thickness (μm) 0.5 0.5 0.5 0.5 Photocatalyticaction 100 48 48 0 Adhesion properties Between substrate and 100/100 50/100 — — first coating layer Between first coating  20/100  98/100 —— layer and second coating layer Between substrate and — —  30/100 40/100 second coating layer Hardness Contact Angle <2 B 4 H 4 H 6 HInitial stage 49° 71° 72° 76° After UV irradiation <10° <10° <10° 75°Deterioration of coating None None None None Deterioration of substrateSome None None None (Discolor- ation)

TABLE 4 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Coated product Func.(11) Func. (12) Func. (13) Func. (14) Func. (15) Func. (16) Substrate PCplate PC plate PC plate PC plate PC plate PC plate First coating layerCoating Acryl- Acryl- Acryl- Acryl- Acryl- Acryl- material modifiedmodified modified modified modified modified silicone silicone siliconesilicone silicone silicone resin (1) + resin (1) + resin (1) + resin(1) + resin (1) + resin (1) + Pigment Pigment Pigment Pigment PigmentPigment 1 2 3 1 2 3 Coating thickness (μm) 1 1 1 1 1 1 Second coatinglayer Coating Func. Func. Func. Func. Func. Func. material (1-3) (1-3)(1-3) (2-3) (2-3) (2-3) Resin solid content/ 50/50 50/50 50/50 50/5050/50 50/50 photocatalyst (weight ratio) Coating thickness (μm) 0.5 0.50.5 0.5 0.5 0.5 Photocatalytic action 47 49 47 44 46 47 Adhesionproperties Between substrate and 100/100 100/100 100/100 100/100 100/100100/100 first coating layer Between first coating 100/100 100/100100/100 100/100 100/100 100/100 layer and second coating layer HardnessContact Angle 4 H 4 H 4 H 4 H 4 H 4 H Initial stage 70° 71° 71° 78° 78°78° After UV irradiation <10° <10° <10° <10° <10° <10° Deterioration ofcoating None None None None None None Deterioration of substrate NoneNone None None None None

TABLE 5 Ex. 17 Ex. 18 Comp. Ex. 7 Coated product Func. (17) Func. (18)Comp. (7) Substrate PC plate PC plate PC plate First coating layerCoating Acryl- Acryl- Acryl- material modified modified modifiedsilicone silicone silicone resin (1) resin (1) resin (1) Coatingthickness (μm) 1 1 1 Second coating layer Coating Func. Func. Comp.material (1-3) (2-3) (1) Resin solid content/ 50/50 50/50 100/0photocatalyst (weight ratio) Coating thickness (μm) 0.1 0.1 0.1Photocatalytic action 33 30 0 Adhesion properties Between substrate and100/100 100/100 100/100 first coating layer Between first coating100/100 100/100 100/100 layer and second coating layer Hardness ContactAngle 4 H 4 H 5 H Initial stage 74° 78° 75° After UV irradiation <10°<10° 75° Deterioration of coating None None None Deterioration ofsubstrate None None None

TABLE 6 Ex. 19 Ex. 20 Coated product Func. (19) Func. (20) Substrate PCplate PC plate First coating layer Coating Acryl-modified Acryl-modifiedmaterial silicone silicone resin (2) resin (3) Coating thickness (μm) 11 Second coating layer Coating Func. Func. material (1-3) (2-3) Resinsolid content/ 50/50 50/50 photocatalyst (weight ratio) Coatingthickness (μm) 0.5 0.5 Photocatalytic action 48 46 Adhesion propertiesBetween substrate and 100/100 100/100 first coating layer Between firstcoating 100/100 100/100 layer and second coating layer Hardness ContactAngle 4 H 4 H Initial stage 70° 79° After UV irradiation <10° <10°Deterioration of coating None None Deterioration of substrate None None

TABLE 7 Comp. Comp. Ex. 21 Ex. 22 Ex. 8 Ex. 23 Ex. 24 Ex. 9 Coatedproduct Func. (21) Func. (22) Comp. (8) Func. (23) Func. (24) Comp. (9)Substrate PVC plate PVC plate PVC plate Organic- Organic- Organic-coated coated coated First coating layer Coating Acryl- Acryl- — Acryl-Acryl- — material modified modified modified modified silicone siliconesilicone silicone resin (1) resin (1) resin (1) resin (1) Coatingthickness (μm) 1 1 — 1 1 — Second coating layer Coating Func. Func.Func. Func. Func. Func. material (1-3) (2-3) (1-3) (1-3) (2-3) (1-3)Resin solid content/ 50/50 50/50 50/50 50/50 50/50 50/50 photocatalyst(weight ratio) Coating thickness (μm) 0.5 0.5 0.5 0.5 0.5 0.5Photocatalytic action 49 47 48 48 46 48 Adhesion properties Betweensubstrate and 100/100 100/100 — 100/100 100/100 — first coating layerBetween first coating 100/100 100/100 — 100/100 100/100 — layer andsecond coating layer Between substrate and — —  25/100 — —  30/100second coating layer Hardness Contact Angle 4 H 4 H 4 H 4 H 4 H 3 HInitial stage 70° 80° 72° 72° 78° 72° After UV irradiation <10° <10°<10° <10° <10° <10° Deterioration of coating None None None None NoneNone Deterioration of substrate None None None None None None

TABLE 8 Comp. Ex. 25 Ex. 26 Ex. 10 Ex. 27 Ex. 28 Coated pro- Func. (25)Func. (26) Comp. Func. (27) Func. (28) duct Sub- Stainless Stainless(10) Glass Glass strate plate plate Stainless plate plate plate Firstcoating layer Coating Acryl- Acryl- — Acryl- Acryl- material modifiedmodified modified modified silicone silicone silicone silicone resin (1)resin (1) resin (1) resin (1) Coating 1 1 — 1 1 thickness (μm) Secondcoat- ing layer Coating Func. Func. Func. Func. Func. material (1-3)(2-3) (1-3) (1-3) (2-3) Resin solid 50/50 50/50 50/50 50/50 50/50content/ photocatalyst (weight ratio) Coating 0.5 0.5 0.5 0.5 0.5thickness (μm) Photocataly- 47 47 45 47 46 tic action Adhesionproperties Between 100/100 100/100 — 100/100 100/100 substrate and firstcoating layer Between 100/100 100/100 — 100/100 100/100 first coatinglayer and second coat- ing layer Between — —  30/100 — — substrate andsecond coat- ing layer Hardness 4 H 4 H 4 H 4 H 4 H Contact AngleInitial stage 69° 78° 70° 78° 79° After UV <10° <10° <10° <10° <10°irradiation Deterioration None None None None None of coatingDeterioration None None None None None of substrate

TABLE 9 Ex. 29 Ex. 30 Ex. 31 Ex. 32 Coated product Func. (29) Func. (30)Func. (31) Func. (32) Substrate Tile Tile Enamel Enamel plate plateFirst coating layer Coating Acryl- Acryl- Acryl- Acryl- materialmodified modified modified modified silicone silicone silicone siliconeresin (1) resin (1) resin (1) resin (1) Coating thickness (μm) 1 1 1 1Second coating layer Coating Func. Func. Func. Func. material (1-3)(2-3) (1-3) (2-3) Resin solid content/ 50/50 50/50 50/50 50/50photocatalyst (weight ratio) Coating thickness (μm) 0.5 0.5 0.5 0.5photocatalytic action 46 46 46 48 Adhesion properties Between substrateand 100/100 100/100 100/100 100/100 first coating layer Between firstcoating 100/100 100/100 100/100 100/100 layer and second coating layerBetween substrate and — — — — second coating layer Hardness ContactAngle 4 H 4 H 4 H 4 H Initial stage 70° 80° 79° 79° After UV irradiation<10° <10° <10° <10° Deterioration of coating None None None NoneDeterioration of substrate None None None None

TABLE 10 Comp. Ex. 11 Comp. Ex. 12 Coated product Comp. (11) Comp. (12)Substrate PC plate PC plate First coating layer Coating Acryl- Acryl-material modified modified silicone silicone resin (1)*1 resin (1)*2Coating thickness (μm) 1 1 Second coating layer Coating Func. Func.material (1-3) (1-3) Resin solid content/ 50/50 50/50 photocatalyst(weight ratio) Coating thickness (μm) 0.5 Photocatalytic actionImpossible 44 to form second coating layer Adhesion properties Betweensubstrate and  80/100 first coating layer Between first coating 100/100layer and second coating layer Hardness Contact Angle 3 H Initial stage72° After UV irradiation <10° Deterioration of coating Impossible toNone form second coating layer Deterioration of substrate None *1: Afterapplication, baked at 150° C. for 30 minutes. *2: After application,left to stand at room temperature for 10 minutes.

TABLE 11 Ex. 29 Ex. 30 Ex. 33 Ex. 34 Ex. 35 Ex. 36 Coated product Func.(29) Func. (30) Func. (33) Func. (34) Func. (35) Func. (36) substrateTile Tile Tile Tile Tile Tile First coating layer Coating materialAcryl- Acryl- Acryl- Acryl- Acryl- Acryl- modified modified modifiedmodified modified modified silicone silicone silicone silicone siliconesilicone resin (1) resin (1) resin (4) resin (5) resin (6) resin Coatingthickness (μm) 1 1 1 1 1 1 Second coating layer Coating material Func.Func. Func. Func. Func. Func. (1-1) (2-3) (1-3) (1-3) (1-3) (1-3) Resinsolid content/ 50/50 50/50 50/50 50/50 50/50 50/50 photocatalyst (weightratio) Coating thickness (μm) 0.5 0.5 0.5 0.5 0.5 0.5 Photocatalyticaction 46 46 46 46 46 46 Evaulation of accelerated weathering testAdhesion properties Between substrate and first coating layer 2,500 hrs.100/100 100/100 100/100 100/100 100/100 100/100 4,000 hrs. 100/100100/100 100/100 100/100 100/100 100/100 Between first coating layer andsecond coating layer 2,500 hrs. 100/100 100/100 100/100 100/100 100/100100/100 4,000 hrs. 100/100 100/100 100/100 100/100 100/100  90/100Discoloration degree Δ 2,500 hrs. 0.2 0.3 1.8 0.6 3.0 3.5 4,000 hrs. 0.50.6 5.5 1.0 8.0 10.5

TABLE 12 Comp. Comp. Ex. 37 Ex. 38 Ex. 13 Ex. 14 Coated product Func.(37) Func. (38) Comp. (13) Comp. substrate Tile Tile Tile (14) TileFirst coating layer Coating material Acryl- Acryl- Commercially Acryl-modified modified available modified silicone silicone expoxy typesilicone resin (8) resin (9) primer resin (7) Coating thickness 1 1 8 1(μm) Second coating layer Coating material Func. Func. Func. Comp. (1-1)(2-3) (2-3) (1) Resin solid con- 50/50 50/50 50/50 100/0tent/photocatalyst (weight ratio) Coating thickness 0.5 0.5 0.5 0.5 (μm)Photocatalytic 46 46 46 0 action Evaulation of accelerated weather- ingtest Adhesion properties Between substrate and first coating layer 2,500hrs. 100/100 100/100 100/100 100/100 4,000 hrs. 100/100 100/100  50/100100/100 Between first coat- ing layer and second coating layer 2,500hrs. 100/100 100/100  90/100 100/100 4,000 hrs. 100/100 100/100  20/100100/100 Discoloration degree Δ 2,500 hrs. 2.1 2.6 5.4 2.3 4,000 hrs. 6.07.0 30.0 5.7

EFFECT OF THE INVENTION

The functional coated product of the present invention is excellent inadhesion properties of the coating to various substrates for prime coat,and the deterioration of the substrate and the coating due tophotocatalytic action hardly occurs. Further, the smoothness on thesurface of the coating is high and therefore, it hardly has dirt andalso has high photocatalytic action.

In the functional coated product of the present invention, the curedcoating made of the acryl-modified silicone resin coating material isinterposed, as the first coating layer, between the substrate and thecured coating made of the functional coating material containing aphotocatalyst, the substrate is not directly influenced by thephotocatalytic action, even if the substrate is an organic substrate ora substrate coated with an organic substance. Therefore, thedeterioration of the substrate due to the photocatalytic action hardlyoccurs. Further, by the interposition of the first coating layercomprising the cured coating of the above-mentioned acryl-modifiedsilicone resin coating material, the adhesion properties of theabove-mentioned functional coating material to the substrate isimproved.

The functional coating material and an acryl-modified silicone resincoating material to be used in the present invention are both inorganiccoating materials, therefore, the coating thereof is hardly deterioratedeven if it receives the photocatalytic action.

When the functional coated product of the present invention isirradiated by ultraviolet light, dirt such as water-repellant organicsubstances is decomposed by the action of the photocatalyst contained inthe second coating layer, so that wettability of the coating to water isimproved, in addition to the effect of decomposition and deodorizationof organic substances, the antifungal effect, the antimycotic effect,etc. This performance is exhibited regardless of the thickness of thecoating and the amount of the photocatalyst contained therein. If thewettability of the coating to water is high, a defrosting effect, anstainproof effect due to washing action by rain-water in the outdooruse, etc. are exhibited. Accordingly, the functional coated product ofthe present invention also has other performance such as the preventionof moisture condensation on the window glass, etc. in winter, or thestainproof effect of architectural structure, road structure,automobiles, vehicles, etc.

The functional coated product of the present invention shows desirableperformance, even if a pigment is dispersed into the acryl-modifiedsilicone resin coating material which forms the first coating layer.Therefore, it is possible to color the coating with an optional color.

In the functional coating material of the present invention, it ispossible to control coating properties such as photocatalyticperformance, hardness or surface conditions of the coating, depending onthe use, by changing the ratio of the amount of the resin to that of thephotocatalyst.

The coating material to be used for the functional coated product of thepresent invention can be used under dry-curing conditions or thetemperature in the wide range, because it is possible to conduct notonly heat-curing but also cold curing. Therefore, it is possible toapply a coating not only to a substrate having a configuration which isnot easily uniformly heated, a substrate having a large size or asubstrate having poor heat resistance, etc., but also to a place whereheating is not easily conducted, for example, when coating operationsare conducted outdoors. Accordingly, its industrial value is high.

According to the production method of the present invention, theapplication for forming the second coating layer is conducted while thefirst coating layer is in a semi-cured condition. Therefore, it ispossible to conduct the coating process for a short period of time, byselecting temperature conditions, etc. Thus, according to the productionmethod of the present invention, a functional coated product having theabove-mentioned excellent performance can be obtained easily andeffectively.

1. A functional coated product having a first coating layer formed of acured coating of an acryl-modified silicone resin coating materialcomprising the following components (A), (B), (C) and (D) on a surfaceof a substrate, and a second coating layer formed of a cured coating ofa functional coating material comprising the following components (E)and (F), over the first coating layer; Component (A): a silica-dispersedorganosilane oligomer solution obtained by partially hydrolyzing ahydrolyzable organosilane represented by the general formulaR^(1m)SiX_(4-m)  (I) wherein R¹ indicates a monovalent hydrocarbon grouphaving 1 to 8 carbon atoms, which may be the same or different, mindicates an integer of 0 to 3, and X indicates a hydrolyzable group incolloidal silica dispersed in an organic solvent, water or a mixedsolvent of them, under the condition that 0.001 to 0.5 mol of water isused based on 1 mol equivalent of the above-mentioned hydrolyzable group(X); Component (B): a polyorganosiloxane represented by the averagecompositional formulaR² _(a)Si(OH)_(b)O_((4-a-b)/2)  (II) wherein R² indicates a monovalenthydrocarbon group having 1 to 8 carbon atoms, which may be the same ordifferent, a and b separately satisfy the following condition:0.2≦a≦2, 0.0001≦b≦3, a+b<4, which contains a silanol group in themolecule structure and has an average molecular weight (in terms ofpolystyrene) of 700 to 20,000; Component (C): a curing catalyst;Component (D): an acrylic resin of copolymer of first (meth)acrylaterepresented by the general formula (III)CH₂═CR³(COOR⁴)  (III) in which R³ is a hydrogen atom or a methyl group,and R⁴ is a hydrocarbon group having 1 to 9 carbon atoms, the second(meth)acrylate of the general formula (III) in which R³ is a hydrogenatom or a methyl group, and R⁴ is at least one group selected from thegroup consisting of an epoxy group, a glycidyl group, and a hydrocarbongroup containing at least either of the above, and the third(meth)acrylate of the general formula (III) in which R³ is a hydrogenatom or a methyl group, and R⁴ is a hydrocarbon group containing analkoxy silyl group or a halogenated silyl group, and said acrylic resinhaving an average molecular weight (in terms of polystyrene) of 1,000 to50,000; Component (E): an organosiloxane comprising a hydrolyzedpolycondensate of; 5 to 30,000 parts by weight of a silica compoundrepresented by the general formula:Si(OR⁵)₄ and/or colloidal silica, 100 parts by weight of a silicacompound represented by the general formula:R⁶Si(OR⁵)₃ and 0 to 60 parts by weight of a silica compound representedby the general formula:R⁶Si(OR⁵)₂ wherein R⁵ and R⁶ indicate a monovalent hydrocarbon group andsaid weight-average molecular weight being adjusted to 800 or more interms of polystyrene; and Component (F): a photocatalyst.
 2. Thefunctional coated product according to claim 1, wherein, in theabove-mentioned acryl-modified silicone resin coating material, 1 to 94parts by weight of Component (B) and 5 to 35 parts by weight ofComponent (D) are formulated in 1 to 94 parts by weight of Component(A), based on the solid content of the whole condensate (provided thatthe total amount of Components (A), (B) and (D) comes to 100 parts byweight).
 3. The functional coated product according to claim 1, whichfurther contains a pigment.
 4. The functional coated product accordingto claim 1, wherein a substrate is selected from the group consisting ofa metallic substrate, an organic substrate and an organic coatingsubstrate in which either one of the above substrates has a coatingformed from an organic compound on the surface thereof.
 5. A memberrelated to building construction at least a part of which is equippedwith the functional coated product according to claim
 1. 6. A gate for abuilding at least a part of which is equipped with the functional coatedproduct according to claim
 1. 7. The gate for building of claim 6, inwhich the part is a gate pier.
 8. A wall for a building at least a partof which is equipped with the functional coated product according toclaim
 1. 9. The functional coated product according to claim 1, whereinthe substrate is a member for using the gate.
 10. A window at least apart of which is equipped with the functional coated product accordingto claim
 1. 11. The window according to claim 10, which is a lightingwindow.
 12. The window according to claim 10, the part is a windowframe.
 13. An automobile at least a part of which is equipped with thefunctional coated product according to claim
 1. 14. Mechanical equipmenthaving at least a part of which is equipped with the functional coatedproduct according to claim
 1. 15. A member for highway-relatedconstruction at least a part of which is equipped the functional coatedproduct according to claim
 1. 16. The member for highway-relatedconstruction according to claim 15, which is a traffic-control sign, aside wall of the road, an electric-light pole or a protection fence. 17.A post for public notice at least a part of which is equipped with thefunctional coated product according to claim
 1. 18. An illuminator atleast a part of which is equipped with the functional coated productaccording to claim
 1. 19. The functional coated product according toclaim 1, wherein the substrate is a resin material to be used for anilluminator.
 20. The functional coated product according to claim 1,wherein the substrate is a metal material to be used for an illuminator.21. A functional coated product having a first coating layer formed of acured coating of an acryl-modified silicone resin coating materialcomprising the following components (A), (B), (C) and (D) on a surfaceof a substrate, and a second coating layer formed of a cured coating ofa functional coating material comprising the following components (A),(B), (C), (E) and (F), over the first coating layer; Component (A): asilica-dispersed organosilane oligomer solution obtained by partiallyhydrolyzing a hydrolyzable organosilane represented by the generalformulaR¹ _(m)SiX_(4-m)  (I) wherein R¹ indicates a monovalent hydrocarbongroup having 1 to 8 carbon atoms, which may be the same or different, mindicates an integer of 0 to 3, and X indicates a hydrolyzable group incolloidal silica dispersed in an organic solvent, water or at mixedsolvent of them, under the condition that 0.001 to 0.5 mol of water isused based on 1 mol equivalent of the above-mentioned hydrolyzable group(X); Component (B): a polyorganosiloxane represented by the averagecompositional formulaR² _(a)Si(OH)_(b)O_((4-a-b)/2)  (II) wherein R² indicates a monovalenthydrocarbon group having 1 to 8 carbon atoms, which may be the same ordifferent, a and b separately satisfy the following condition:0.2≦a≦2, 0.0001≦b≦3, a+b<4, which contains a silanol group in themolecule structure and has an average molecular weight (in terms ofpolystyrene) of 700 to 20,000; Component (C): a curing catalyst;Component (D): an acrylic resin of copolymer of first (meth)acrylaterepresented by the general formula (III)CH₂═CR³(COOR⁴)  (III) in which R³ is a hydrogen atom or a methyl group,and R⁴ is a hydrocarbon group having 1 to 9 carbon atoms, the second(meth)acrylate of the general formula (III) in which R³ is a hydrogenatom or a methyl group, and R⁴ is at least one group selected from thegroup consisting of an epoxy group, a glycidyl group, and a hydrocarbongroup containing at least either of the above, and the third(meth)acrylate of the general formula (III) in which R³ is a hydrogenatom or a methyl group, and R⁴ is a hydrocarbon group containing analkoxy silyl group or a halogenated silyl group, and said acrylic resinhaving an average molecular weight (in terms of polystyrene) of 1,000 to50,000; Component (E): an organosiloxane comprising a hydrolyzedpolycondensate of; 5 to 30,000 parts by weight of a silica compoundrepresented by the general formula:Si(OR⁵)₄ and/or colloidal silica, 100 parts by weight of a silicacompound represented by the general formula:R⁶Si(OR⁵)₃ and 0 to 60 parts by weight of a silica compound representedby the general formula:R⁶Si(OR⁵)₂ wherein R⁵ and R⁶ indicate a monovalent hydrocarbon group andsaid weight-average molecular weight being adjusted to 800 or more interms of polystyrene; and Component (F): a photocatalyst.
 22. A processfor producing a functional coating material comprising the followingsteps: forming a first coating layer by applying an acryl-modifiedsilicone resin coating material containing the following components (A),(B), (C) and (D) to surface of a substrate, forming a semi-cured layerby semi-curing the first coating layer, forming a second coating layerby applying a functional coating material containing the followingcomponents (E) and (F) to surface of said semi-cured layer, and curingsaid semi-cured layer and said second coating layer; Component (A): asilica-dispersed organosilane oligomer solution obtained by partiallyhydrolyzing a hydrolyzable organosilane represented by the generalformulaR¹ _(m)SiX_(4-m)  (I) wherein R¹ indicates a monovalent hydrocarbongroup having 1 to 8 carbon atoms, which may be the same or different, mindicates an integer of 0 to 3, and X indicates a hydrolyzable group incolloidal silica dispersed in an organic solvent, water or a mixedsolvent of them, under the condition that 0.001 to 0.5 mol of water isused based on 1 mol equivalent of the above-mentioned hydrolyzable group(X); Component (B): a polyorganosiloxane represented by the averagecompositional formulaR² _(a)Si(OH)_(b)O_((4-a-b)/2)  (II) wherein R² indicates a monovalenthydrocarbon group having 1 to 8 carbon atoms, which may be the same ordifferent, a and b separately satisfy the following condition:0.2≦a≦2, 0.0001≦b≦3, a+b<4, which contains a silanol group in themolecule structure and has an average molecular weight (in terms ofpolystyrene) of 700 to 20,000; Component (C): a curing catalyst;Component (D): an acrylic resin of copolymer of first (meth)acrylaterepresented by the general formula (III)  CH₂═CR³(COOR⁴)  (III) in whichR³ is a hydrogen atom or a methyl group, and R⁴ is a hydrocarbon grouphaving 1 to 9 carbon atoms, the second (meth)acrylate of the generalformula (III) in which R³ is a hydrogen atom or a methyl group, and R⁴is at least one group selected from the group consisting of an epoxygroup, a glycidyl group, and a hydrocarbon group containing at leasteither of the above, and the third (meth)acrylate of the general formula(III) in which R³ is a hydrogen atom or a methyl group, and R⁴ is ahydrocarbon group containing an alkoxy silyl group or a halogenatedsilyl group, and said acrylic resin having an average molecular weight(in terms of polystyrene) of 1,000 to 50,000; Component (E): anorganosiloxane comprising a hydrolyzed polycondensate of; 5 to 30,000parts by weight of a silica compound represented by the general formulaSi(OR⁵)₄ and/or colloidal silica, 100 parts by weight of a silicacompound represented by the general formula:R⁶Si(OR⁵)₃ and 0 to 60 parts by weight of a silica compound representedby the general formula:R⁶Si(OR⁵)₂ wherein R⁵ and R⁶ indicate a monovalent hydrocarbon group andsaid weight-average molecular weight being adjusted to 800 or more interms of polystyrene; and Component (F): a photocatalyst.
 23. Theprocess for producing a functional coated product according to claim 22,wherein, in the above-mentioned acryl-modified silicone resin coatingmaterial, 1 to 94 parts by weight of Component (B) and 5 to 35 parts byweight of Component (D) are formulated in 1 to 94 parts by weight ofComponent (A), based on the solid content of the whole condensate(provided that the total amount of Components (A), (B) and (D) comes to100 parts by weight).
 24. The process for producing a functional coatedproduct according to claim 22, which further contains a pigment.
 25. Theprocess for producing a functional coated product according to claim 22,wherein said substrate is selected from the group consisting of ametallic substrate, an organic substrate and an organic coatingsubstrate in which either of the above substrates has a coating formedfrom an organic substance on the surface thereof.
 26. A process forproducing a functional coating material comprising the following steps:forming a first coating layer by applying an acryl-modified siliconeresin coating material containing the following components (A), (B), (C)and (D) to surface of a substrate, forming a semi-cured layer bysemi-curing the first coating layer, forming a second coating layer byapplying a functional coating material containing the followingcomponents (A), (B), (C) and (F) to surface of said semi-cured layer,and curing said semi-cured layer and said second coating layer;Component (A): a silica-dispersed organosilane oligomer solutionobtained by partially hydrolyzing a hydrolyzable organosilanerepresented by the general formulaR¹ _(m)SiX_(4-m)  (I) wherein R¹ indicates a monovalent hydrocarbongroup having 1 to 8 carbon atoms, which may be the same or different, mindicates an integer of 0 to 3, and X indicates a hydrolyzable group incolloidal silica dispersed in an organic solvent, water or a mixedsolvent of them, under the condition that 0.001 to 0.5 mol of water isused based on 1 mol equivalent of the above-mentioned hydrolyzable group(X); Component (B): a polyorganosiloxane represented by the averagecompositional formulaR² _(a)Si(OH)_(b)O_((4-a-b)/2)  (II) wherein R² indicates a monovalenthydrocarbon group having 1 to 8 carbon atoms, which may be the same ordifferent, a and b separately satisfy the following condition:0.2≦a≦2, 0.0001≦b≦3, a+b<4, which contains a silanol group in themolecule structure and has an average molecular weight (in terms ofpolystyrene) of 700 to 20,000; Component (C): a curing catalyst;Component (D): an acrylic resin of copolymer of first (meth)acrylaterepresented by the general formula (III)CH₂═CR³(COOR⁴)  (III) in which R³ is a hydrogen atom or a methyl group,and R⁴ is a hydrocarbon group having 1 to 9 carbon atoms, the second(meth)acrylate of the general formula (III) in which R³ is a hydrogenatom or a methyl group, and R⁴ is at least one group selected from thegroup consisting of an epoxy group, a glycidyl group, and a hydrocarbongroup containing at least either of the above, and the third(meth)acrylate of the general formula (III) in which R³ is a hydrogenatom or a methyl group, and R⁴ is a hydrocarbon group containing analkoxy silyl group or a halogenated silyl group, and said acrylic resinhaving an average molecular weight (in terms of polystyrene) of 1,000 to50,000; Component (E): an organosiloxane comprising a hydrolyzedpolycondensate of; 5 to 30,000 parts by weight of a silica compoundrepresented by the general formula:Si(OR⁵)₄ and/or colloidal silica, 100 parts by weight of a silicacompound represented by the general formula:R⁶Si(OR⁵)₃ and 0 to 60 parts by weight of a silica compound representedby the general formula:R⁶Si(OR⁵)₂ wherein R⁵ and R⁶ indicate a monovalent hydrocarbon group andsaid weight-average molecular weight being adjusted to 800 or more interms of polystyrene; and Component (F): a photocatalyst.